Chemical Reduction of 2,4,6-Tricyano-1,3,5-triazine and

1,3,5-Tricyanobenzene. Formation of Novel

4,4,6,6-Tetracyano-2,2-bitriazine and Its Radical Anion

Ri co E. Del Sesto,

Atta M. Ari f,

Juan J. Novoa,

I wona Anusi ewi cz,

|
Pi otr Skurski ,
|
Jack Si mons,

Bri an C. Dunn,

Edward M. Eyri ng,

and Joel S. Mi l l er*

,
Department of Chemistry, University of Utah, 315 S. 1400 E. RM 2124, Salt LakeCity, Utah 84112-0850,
Department of Chemistry, University of Gdansk, 80-952 Gdansk, Poland, and theDepartment of Physical
Chemistry, University of Barcelona, Av. Diagonal, 647, E-08028, Barcelona, Spain
jsmiller@chemistry.utah.edu
Received April 17, 2002
Chemi cal reducti on of 2,4,6-tri cyano-1,3,5-tri azi ne, TCT, resul ts i n the formati on of an unstabl e
radi cal ani on that undergoes i mmedi ate di meri zati on at a ri ng carbon to form [C
12
N
12
]
2-
, [TCT]
2
2-
,
characteri zed by a l ong 1.570 (4) central C-C bond. [TCT]
2
2-
can decompose i nto the radi cal
ani on of 4,4,6,6-tetracyano-2,2-bi tri azi ne, [TCBT]
-
, the one-el ectron reduced form of pl anar (D
2h
)
TCBT, whi ch i s al so structural l y characteri zed as the [TMPD][TCBT] charge-transfer compl ex
(TMPD )N,N,N,N-tetramethyl -p-phenyl enedi ami ne) wi th a 1.492 (2) central sp
2
-sp
2
C-C bond.
Al though crystal s coul d not be obtai ned for the radi cal ani on [TCBT]
-
, the el ectrochemi stry (E )
+0.03 V), EPR (g ) 2.003,
2
A
14
N
) 3.347 G, and
4
A
14
N
) 0.765 G and a l i ne wi dth of 0.24 G), and
theoreti cal cal cul ati ons support the formati on of [TCBT]
-
. I n addi ti on, thermol ysi s of [TCT]
2
2-
yi el ds [TCBT]
-
. Chemi cal reducti on of 2,4,6-tri cyanobenzene, TCB, forms an unstabl e radi cal ani on
that i mmedi atel y undergoes di meri zati on at a ri ng carbon to form [C
12
H
6
N
6
]
2-
, [TCB]
2
2-
, whi ch
has a l ong 1.560 (5) central C-C bond. Reacti on of TCT wi th tetrathi aful val ene (TTF) forms
structural l y characteri zed [TTF][TCT], and i n the presence of water, TCThydrol yzes to 2,4-di cyano-
6-hydroxy-s-tri azi ne, DCTOH. I n contrast, the reacti on of TCT wi th TMPD forms [TMPD][TCT],
whi ch i n the presence of water forms structural l y characteri zed [HTMPD]
+
[DCTO]
-
.
Introduction
The broad cl ass of substi tuted s-tri azi nes are i mportant
i n el ectroni c and pol ymeri c materi al s
1
i n areas of organi c
and catal ysi s chemi stry.
2
Essenti al l y al l 2,4,6-subsi tuted
s-tri azi nes substi tuted thus far have el ectron-rel easi ng/
-donati ng groups, e.g., ami no, al kyl , aryl , al koxy/aryl oxy,
and hal i des. El ectron-wi thdrawi ng groups are not com-
mon because the resonance of the tri azi ne ri ng l ocal i zes
the el ectrons more on the ni trogens than on the carbons;
thus, substi tuti on on the ri ng carbons wi th el ectron-
wi thdrawi ng groups resul ts i n mol ecul es that are ex-
tremel y sensi ti ve to nucl eophi l i c substi tuti on, parti cu-
l arl y hydrol ysi s i n the presence of even trace atmospheri c
water.
3,4
2,4,6-Tri cyano-1,3,5-tri azi ne, TCT, i s a parti cul arl y
i nteresti ng as i t i s ni trogen-ri ch
5
and a tri mer of cyanogen
and an i nteresti ng new acceptor for the devel opment of
mol ecul e-based magnets and conductors. I n thi s regard,
TCT forms a charge-transfer compl ex wi th tetrathi aful -
val ene (TTF), whi ch after exposure to ai r exhi bi ts rel a-
ti vel y hi gh dc el ectri cal conducti vi ty.
6
Furthermore, as a
cyanocarbon, the ni tri l es can coordi nate to metal s and

Dedi cated to Prof. Morti mer M. Labes for hi s pi oneeri ng work i n

the area of azacarbon chemi stry.

Uni versi ty of Utah.

Uni versi ty of Barcel ona.

|
Uni versi ty of Gdansk.
(1) (a) Chang, Y.; Ki m, Y. N.; Noh, I .; Ki m, C. Macromol. Chem.
Phys. 2000, 201, 1802. (b) Fi nk, R.; Hei schkel , Y.; Thel akkat, M.;
Schmi dt, H.-W.; Jonda, C.; Huppauff, M. Chem. Mater. 1998, 10, 3620.
(c) Fi nk, R.; Frenz, C.; Thel akkat, M.; Schmi dt., H.-W. Macromolecules
1997, 30, 8177.
(2) (a) Forbes, D. C.; Barrett, E. J.; Lewi s, D. L.; Smi th, M. C.
Tetrahedron Lett. 2000, 9943. (b) Venkataraman, K.; Wagl e, D. R.
Tetrahedron Lett. 1979, 3037.
(3) (a) Smol i n, E. M.; Rapoport, L. The Chemistry of Heterocyclic
Compounds: s-Triazinesand Derivatives; I ntersci ence Publ i shers: New
York, 1959; Vol . 13. (b) Qui rke, J. M. E. ComprehensiveHeterocyclic
Chemistry, 1984, 3, 457 and references ci ted therei n.
(4) Qui rke, J. M. E. Compr. Heterocycl. Chem. 1984, 3, 457 and
references ci ted therei n.
(5) Subrayan, R. P.; Rasmussen, P. G. Trends Polym. Sci. 1995, 3,
165.
Copyright 2003 by theAmerican Chemical Society
VOLUME 68, NUMBER 9 MAY 2, 2003
10.1021/jo025833h CCC: $25.00 2003 Ameri can Chemi cal Soci ety
J . Org. Chem. 2003, 68, 3367-3379 3367 Publ i shed on Web 12/10/2002
addi ti onal l y gi ve the mol ecul e the capaci ty to accept
el ectrons and become reduced to the radi cal ani oni c
speci es.
TCThas been reported to undergo an i rreversi bl e one-
el ectron reducti on wi th Na or K to form 1
-
.
7
The i n si tu-
generated EPR spectra suggested two sets of equi val ent
ni trogen atoms i n a 2:4 rati o, not by two sets of equi val ent
ni trogen atoms i n a 3:3 rati o as expected for TCT
-
.
However, the number of bonds that need to be broken
and created makes formati on of 1
-
, vi a the reducti on of
TCT, dubi ous, whi ch l ed to the possi bi l i ty of a Jahn-
Tel l er di storti on of TCT
-
as suggested by Carri ngton et
al .
7
As our and previ ous groups attempts to i sol ate any
speci es vi a el ectrochemi cal methods fai l ed,
7
we report
herei n the products that resul t from the chemi cal reduc-
ti on of TCT and the structural l y rel ated 1,3,5-tri cy-
anobenzene, TCB. The reducti ve di meri zati on of TCB was
previ ousl y proposed to form 2
2-
.
8
Prel i mi nary work i n our
l aboratory,
9
however, reveal ed that 2
2-
i s not the reduc-
ti on product of TCB. We al so note that reducti on of TCT
al so l eads to the formati on of redox-acti ve 4,4,6,6-
tetracyano-2,2-bi tri azi ne, TCBT, whose radi cal ani on i s
the source of the EPR spectra previ ousl y reported for the
product of the al kal i metal reducti on of TCT.
Results and Discussion
Electrochemistry of TCT and TCB. The cycl i c
vol tammogram (CV) of TCT, shows an i rreversi bl e reduc-
ti on at -0.39 V (vs SCE) and an i rreversi bl e oxi dati on
at +0.70 V,
9
Fi gure 1a. Al though TCT undergoes a one-
el ectron reducti on, i t requi res a much stronger reduci ng
agent than typi cal cyanocarbon acceptors, e.g., TCNE and
TCNQ.
10
The el ectrochemi cal behavi or of TCB i s anal o-
gous to that of TCT, but wi th an i rreversi bl e reducti on
at -1.35 V and an i rreversi bl e oxi dati on at -0.03 V (vs
SCE), Fi gure 1b. Hence, TCB i s 0.96 V more di ffi cul t to
reduce than TCT. None of the vol tammograms of TCT
or TCB showed any si gn of reversi bl e behavi or for ei ther
reducti ons or oxi dati ons at scan rates of 5-2000 mV/s,
suggesti ng that the i rreversi bi l i ty of the reducti on may
be due to a chemi cal reacti on that i s much faster than
the el ectron-transfer process of the cycl i c vol tammetry.
Chemical Reactions and Reduction of TCT. To
form charge-transfer compl exes and el ectron-transfer
sal ts, TCT was reacted wi th tetrathi aful val ene (TTF)
(E
1/2
) +0.30 V vs SCE i n MeCN),
10
N,N,N,N-tetra-
methyl -p-phenyl enedi ami ne (TMPD) (E
1/2
) +0.10 and
0.72 V),
11
bi s(mesi tyl ene)chromi um(0), Cr(mes)
2
(E
1/2
)
(6) Berl i n, A.; Pagani , G. A.; Sanni col o, F. Synth. Met. 1987, 19, 415.
(b) Berl i n, A.; Pagani , G. A.; Sanni col o, F. J . Chem. Soc., Chem.
Commun. 1986, 1579.
(7) Carri ngton, A.; Longuet-Hi ggi ns, H. C.; Todd, P. F. Mol. Phys.
1965, 9, 211.
(8) Sertel , M.; Yi l di z, A.; Gambert, R.; Baumgarten, H. Electrochim.
Acta 1986, 31, 1287.
(9) Del Sesto, R. E.; Ari f, A. M.; Mi l l er, J. S. Chem. Commun. 2001,
2730. (10) Ward, M. D. Electroanal. Chem. 1989, 16, 181.
FIGURE 1. Cycl i c vol tammograms at 100 mV/s i n MeCN for
(a) TCT, (b) TCB, (c) [TMPD][TCT], (d) {[Cr(mes)2]
+
}2[TCT]2
2-
,
(e) [TMPD][TCBT], and (f) [TDAE]
2+
{[TCBT]
-
}2.
Del Sesto et al .
3368 J . Org. Chem., Vol. 68, No. 9, 2003
-0.92 V),
12
Co
I I
Cp*
2
(Cp* ) pentamethyl cycl opentadi -
enei de) (E
1/2
) -1.47 V),
13
and the two-el ectron donor
tetraki s(di methyl ami no)ethyl ene, TDAE (E
1/2
) -0.53
and -0.68 V).
14
The -0.39 V i rreversi bl e reducti on
potenti al for TCT requi res strong reduci ng agents for
el ectron transfer to occur and thi s i s onl y expected for
the l atter three el ectron donors.
Reaction of TCT with TMPD. The reacti on of TCT
wi th TMPD i n MeCN l eads to several products, i ncl udi ng
[TMPD][TCT]. Al though crystal s sui tabl e for the si ngl e-
crystal structural determi nati on of [TMPD][TCT] were
not obtai ned, the el ectroni c absorpti on spectrum of the
sol i d [TMPD][TCT] has an absorpti on at 10 000 cm
-1
(1000 nm), whi ch i s assi gned to the TMPD fTCTcharge
transfer (Fi gure 2a). Li kewi se, the I R spectrum shows
peaks predomi nantl y from the two i ndependent neutral
speci es. Hence, el ectron transfer does not occur i n ei ther
sol uti on or i n the sol i d state. Thi s i s confi rmed as the
CV of [TMPD][TCT] shows the i rreversi bl e reducti on of
TCT at -0.39 V i n addi ti on to the two one-el ectron
oxi dati ons of TMPD (Fi gure 1c).
TMPD was reacted wi th TCTi n MeCN contai ni ng 5%
water, and a yel l ow preci pi tate of [TMPD][DCTOH]
composi ti on formed, whose structure was determi ned.
The si ngl e-crystal X-ray anal ysi s shows that, as sug-
gested for [TTF][TCT],
6
the nucl eophi l i c di spl acement of
one of the ni tri l es by water fol l owed by a proton transfer
(aci d-base reacti on) from the resul ti ng 2,4-di cyano-6-
hydroxy-s-tri azi ne, DCTOH, to one of the TMPD ni tro-
gens occurred. The presence of [HTMPD]
+
i s based on
the twi st of the di methyl ami no group on N7 bei ng 90
out of the pl ane of the benzene ri ng, Fi gure 3, and the
average bond angl e around N7 i s 109.4, i ndi cati ng sp
3
hybri di zati on. Thi s i s i nconsi stent wi th the expected
pl anari ty of the TMPD mol ecul e i n i ts neutral state.
Though the proton posi ti on was refi ned as bei ng bonded
to an sp
3
-hybri di zed N7, i t i s expected that the 2,4-
di cyano-6-hydroxy-s-tri azi ne woul d be fai rl y aci di c con-
si deri ng the el ectronegati vi ty of the tri azi ne ri ng.
2,4,15
The ani oni c charge i n [DCTO]
-
i s l ocated wi thi n the ri ng,
and the resul ti ng ketone i s H-bonded to the [HTMPD]
+
,
on the basi s of the ri ng angl e on N2 bei ng 109.3 and
the angl es around C1 averagi ng 120. Hence, the struc-
ture i s best descri bed as [HTMPD]
+
[DCTO]
-
, Fi gure 3.
Cal cul ati ons were carri ed out on [DCTO]
-
at the RHF/
6-31++G** l evel usi ng the atomi c coordi nates from the
crystal structure of [HTMPD]
+
[DCTO]
-
. The cal cul ati ons
show that the b
1
HOMO l i es 10.737 eV bel ow the a
1
LUMO, Fi gure 4, and the el ectron densi ty pri nci pal l y
resi des on the i mi de N, wi th respect to the O, Fi gure 4c,
Tabl e 1.
Reaction of TCT with TTF. TCT forms a charge-
transfer compl ex wi th tetrathi aful val ene, TTF.
6
Si ngl e-
crystal X-ray anal ysi s shows that the structure of [TTF]-
[TCT] i s compri sed of stacks of al ternati ng TTF and TCT
i n a DADA (D ) TTF; A ) TCT) moti f (Fi gure 5).
16
The central CdC bond of the TTF fragment i s 1.348 ,
and i nner C-S bonds are 1.756 . The [TTF][TCT] i s
di amagneti c, and the bond l engths are comparabl e to
neutral TTF
17a
and other charge-transfer compl exes of
TTF wi th CdC bond l engths of 1.35 and C-S bonds
l engths of 1.76 .
17
These bond l engths make the TTF
0
di sti ngui shabl e from the radi cal cati on and/or parti al l y
charged TTF, whi ch typi cal l y have CdC bonds of 1.404
and C-S bonds 1.713 , as seen i n [TTF][Cl O
4
]
17b
or
[TTF][SCN]
0.57
.
17d
Hence, [TTF][TCT] i s a charge transfer
compl ex and not an el ectron transfer sal t, as i ni ti al l y
formul ated but not structural l y characteri zed.
6
The bul k
of the TCTri ng overl aps wi th one ri ng of TTF. The cl osest
contact between the two moi eti es i s 3.17 . The TTF and
TCT pl anes are not paral l el wi thi n a stack, devi ati ng by
8 from each other. The angl e between the TTF i n one
stack to TCT i n an adjacent stack i s 45.
The UV/vi si bl e/NI R spectrum for the [TTF][TCT] i n
MeCN i s the sum of the sol uti on spectra for TTF and
(11) Tanaka, S.; Bruce, J. A.; Wri ghton, M. S. J . Phys. Chem. 1981,
85, 3779.
(12) Yureva, L. P.; Peregudova, S. M.; Kravtsov, D. N.; Vasi l kov,
A. Yu.; Neki asov, L. N.; Asfandi arov, N. L.; Ti moshenko, M. M.; Chi sov,
Yu. V. J . Organomet. Chem. 1987, 336, 371.
(13) Robbi ns, J. L.; Edel stei n, N.; Spencer, B.; Smart, J. C. J . Am.
Chem. Soc. 1982, 104, 1882.
(14) Bock, H.; Borrmann, H.; Havl as, Z.; Oberhammer, H.; Ruppert,
K.; Si mon, A. Angew. Chem., I nt. Ed. 1991, 30, 1678.
(15) Wi l mshurst, J. K. J . Chem. Phys. 1958, 28, 733.
(16) Del Sesto, R. E.; Botoshansky, M.; Kaftory, M.; Ari f, A. M.;
Mi l l er, J. S. Cryst. Eng. Commun. 2002, 4, 117.
(17) (a) Coppens, W. F.; Kenney, N. C.; Edmonds, J. C.; Nagel , A.;
Wudl , F.; Coppens, P. Chem. Commun. 1971, 889. (b) Yakushi , K.;
Ni shi mura, S.; Sugano, T.; Kuroda, H. Acta Crystallogr., Sect. B 1980,
36, 358. (c) Formi gue, M.; Boubekeur, K.; Batai l , P.; Renouard, J.;
Jacob, G. New J . Chem. 1998, 845. (d) Formi gue, M.; Boubekeur, K.;
Batai l , P.; Renouard, J.; Jacob, G. New J . Chem. 1998, 845. (e)
Cl emente, D. A.; Marzotto, A. J . Mater. Chem. 1996, 6, 941.
FIGURE 2. Sol i d-state UV/vi si bl e/NI R spectra of (a) TTF
o
(sol i d l i ne) (b) [TTF][TCT] (dashed l i ne), and (c) [TMPD][TCT]
(dotted l i ne) as pressed KBr pel l ets.
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3369
TCT. However, i n the sol i d state, as a pressed KBr pel l et,
a new absorpti on appears at 10 000 cm
-1
(1000 nm),
whi ch i s assi gned to a TTF f TCT charge transfer (CT)
band as observed for [TMPD][TCT], Fi gure 2. The I R
spectrum al so shows peaks predomi nantl y from the two
i ndependent neutral speci es, wi th sl i ght shi fts i n the
ni tri l e regi on of the TCT, as wel l as i n the
CdN
(TCT)
and
C-S
regi ons. Hence, el ectron transfer does not occur
ei ther i n sol uti on or i n the sol i d state. Thi s i s consi stent
wi th the reported l ow dc el ectri cal conducti vi ty for [TTF]-
[TCT].
6
Upon exposure to the ambi ent l aboratory atmosphere,
[TTF][TCT] turns deep red formi ng a materi al that
exhi bi ts si gni fi cantl y hi gher el ectri cal conducti vi ty (
0.5 S/cm).
6
Al though unabl e to obtai n a structure of the
hydrol ysi s product of [TTF][TCT], on the basi s of I R
spectral changes, i t was proposed that a ni tri l e on TCT
i s substi tuted by -OH from the water, wi th the l oss of
HCN, formi ng deep red [TTF][DCTOH]
6
or, by anal ogy
to the above reacti on wi th TMPD, possi bl y [HTTF]
+
-
[DCTO]
-
. The l atter, however, i s unl i kel y because the
DCTOH
OH
absorpti on (3300 cm
-1
) i s observed i n the
I R spectrum of [TTF][DCTOH] but i s absent i n the
[TMPD]
+
[DCTO]
-
. Si nce TTF i s a poor proton acceptor
and much l ess basi c than TMPD,
18
proton transfer from
thi s hydroxytri azi ne to TTF does not occur as i t does for
[TMPD][DCTOH]. The absence of proton transfer i s al so
consi stent wi th the absence of a shi ft i n the absorpti ons
of the I R of the TTF moi ety, as wel l as the l ack of a shi ft
i n the UV/vi si bl e absorpti on bands.
Reduction of TCT with Cr(mes)
2
, CoCp*
2
, and
TDAE. The reacti on of TCT wi th Cr(mes)
2
l ed to the
formati on of a product whose structure was determi ned
to consi st of the -di mer of [TCT]
-
, [C
12
N
12
]
2-
, [TCT]
2
2-
(Fi gure 6a).
9
[TCT]
2
2-
i s a consti tuti onal i somer of previ -
ousl y reported [C
12
N
12
]
2-
.
19
The structure of the [Cr-
(mes)
2
]
2
[TCT]
2
has a 1.570 (4) -bond formed between
two of the substi tuted tri azi ne-ri ng carbons. Each tri azi ne
ri ng mai ntai ns i ts pl anari ty, suggesti ng that the di mer-
(18) Attanasi o, D.; Bonami co, M.; Fares, V.; Suber, L. J . Chem. Soc.,
Dalton Trans. 1992, 2523.
(19) (a) Buschmann, W. E.; Ari f, A. M.; Mi l l er, J. S. J . Chem. Soc.,
Chem. Commun. 1995, 2343. (b) Manson, J. L.; Buschmann, W. E.;
Mi l l er, J. S. I norg. Chem. 2001, 40, 1926.
FIGURE 3. Structure of [HTMPD]
+
[DCTO]
-
. Bond angl es around N6 range from 108.1(1) for C6-N7-H7 to 112.44(11) for
C6-N7-C12. Bond l engths of the tri azi ne ri ng are 1.242(3) for C1-O1, 1.383(3) for C1-N1, 1.319(3) for C1-N2, 1.337(3)
for C2-N2, 1.337(3) for N2-C3, 1.310(3) for C3-N3, and 1.392(3) for N3-C1. Bond angl e for N1-C1-N3 i s 120.9(2), and
that for C2-N2-C3 i s 109.9(2).
FIGURE 4. HOMO (a), LUMO (b), and cal cul ated charge
densi ty (c) for [DCTO]
-
, where red and bl ue represent negati ve
(-) and posi ti ve (+) potenti al s, respecti vel y. Contour spaci ng
for the orbi tal s i s 0.03, and the el ectrostati c potenti al i s
0.01250 e
-
.
FIGURE 5. Structure of [TTF][TCT] showi ng the overl ap of
TTF (l i ght-col ored spheres, wi th whi te as sul fur and gray as
carbon atoms) and TCT ri ngs (bl ack spheres).
Del Sesto et al .
3370 J . Org. Chem., Vol. 68, No. 9, 2003
i zed carbons are predomi nantl y of sp
2
character. Bond
l engths wi thi n the tri azi ne ri ngs are 1.463(3) for C39-
N2, 1.467(3) for C39-N3, 1.285(3) for C37-N3,
1.348(3) for C37-N1, 1.350(3) for C38-N1, and
1.289(3) for C38-N2. The I R spectrum for thi s sal t
exhi bi ts peaks at 1580, 1320, and 910 cm
-1
as wel l as

CN
at 2242 cm
-1
. The 1580 cm
-1
peak i s assi gned to the
ri ng CdN stretchi ng mode that i s bl ue shi fted wi th
respect to that observed for TCTdue to the ani oni c charge
resi di ng wi thi n the ri ng.
Reacti on of CoCp*
2
and TDAE wi th TCT l eads to
compounds of [CoCp*
2
][TCT] and [TDAE][TCT]
2
compo-
si ti on, respecti vel y. Al l three reducti on products of TCT
di spl ay characteri sti c peaks i n the I R spectrum at 1580,
1320, and 910 cm
-1
, and, hence, al so possess [TCT]
2
2-
.
The el ectrochemi cal behavi or of al l three sal ts of
[TCT]
2
2-
i s the same wi th an i rreversi bl e oxi dati on
occurri ng at +0.70 V, Fi gure 1d, i n addi ti on to the
reversi bl e reducti ons of the cati ons. The i rreversi bl e
oxi dati on i s al so seen i n the CV of TCT, Fi gure 1a. Thi s
anodi c peak i s therefore attri buted to the oxi dati on of
[TCT]
2
2-
to [TCT]
2
-
, whi ch i s unstabl e and breaks apart
i nto [TCT]
-
and TCT
0
, Scheme 1. The i rreversi bl e
reducti on of TCT
0
can then be expl ai ned through the
process of di meri zati on, and suggests that the radi cal
ani on [TCT]
-
i s not stabl e i n the sol vents used (MeCN,
CH
2
Cl
2
, THF) and i mmedi atel y di meri zes to [TCT]
2
2-
,
Scheme 1.
Reaction of TCB with CoCp*
2
. Gi ven the structural
si mi l ari ty of TCB wi th TCT and that the reducti on of
TCB was postul ated to form 2
2-
wi th a framework si mi l ar
to [TCT]
2
2-
,
8
we tri ed to i sol ate the TCB reducti on
product. The reducti on potenti al of TCB i s 0.96 V more
negati ve than that of TCT and shoul d onl y occur upon
reacti on wi th CoCp*
2
of the reductants avai l abl e to us.
Thi s reacti on l ed to the i sol ati on of a compound of
[CoCp*
2
][TCB] composi ti on, whose structure was deter-
mined to be {[CoCp*
2
]
+
}
2
[TCB]
2
2-
, Figure 6b. The [TCB]
2
2-
di ani on resul ts from di meri zati on at the nonsubsti tuted
ri ng carbon, whi ch i s at vari ance wi th the proposed
structure of 2
2-
. [TCB]
2
2-
has a central C-C bond of 1.560
(5) , and the bond l engths wi thi n the benzene ri ngs are
C50-C51, 1.509(4) ; C51-C52, 1.362(4) ; C52-C53,
1.424(4) ; C53-C54, 1.405(4) ; C54-C55, 1.364(3) ;
and C55-C50, 1.523(3) . There i s a shi ft of the ri ng
TABLE 1. Net Atomic Charges Obtained after a
Mulliken Population Analysis of the Density Functional
B3LYP/6-31++G(2d,2p) Wavefunction on Atoms of
Neutral and Radical Anionic [TCT]
n
and [TCBT]
n
(n ) 0, 1-)
mol ecul e atom
charge (e
-
)
n ) 0
charge (e
-
)
n ) 1-
spi n (e
-
)
n ) 1-
[TCT]
n
C1 0.921 0.914 -0.04
C2, C3 0.921 0.924 0.26
C4 -0.591 -0.634 0.00
C5, C6 -0.591 -0.648 -0.04
N1, N3 -0.112 -0.285 0.23
N2 -0.112 -0.134 -0.10
N4 -0.218 -0.337 -0.02
N5, N6 -0.218 -0.395 0.13
[TCBT]
n
C1 -0.203 -0.212 0.314
C2, C3 0.613 0.615 0.029
N1, N3 -0.194 -0.244 0.121
N2 -0.223 -0.301 0.033
C4, C5 0.159 0.100 0.001
N4, N5 -0.366 -0.466 0.003
[DCTO]
-
N1 -1.040
N2, N3 -1.052
N4, N5 -0.508
C1, C2 0.960
C3 1.415
C4, C5 0.312
O -0.797
FIGURE 6. Structure of (a) [TCT]2
2-
as observed i n the [Cr-
(mes)2]2[TCT]2 s-dimer and (b) [TCB]2
2-
as observed in [CoCp*2]2-
[TCB]2, wi th central di mer bonds of 1.570 (4) and 1.560 (5)
, respecti vel y. Li ghter spheres are carbon, darker spheres
ni trogen, and whi te spheres hydrogen.
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3371

CdC
stretch at 1430 cm
-1
i n TCB to 1497 cm
-1
i n
[TCB]
2
2-
, agai n i ndi cati ng that there i s a negati ve charge
wi thi n the ri ng, as observed for [TCT]
2
2-
. The C-H
stretch di sappears upon reducti on; however, an expected
new peak does not appear. The [TCB]
-
di meri zati on at
the unsubsti tuted carbons, as opposed to the ni tri l e-
substi tuted carbons, i s due to the spi n densi ty of the
radi cal ani on bei ng the greatest at the unsubsti tuted
carbons. Thi s most l i kel y forms a ki neti cal l y stabi l i zed
product as i t preci pi tates i mmedi atel y upon the reducti on
of TCB wi th CoCp*
2
.
20
[TCB]
2
2-
can be oxi di zed to TCB
0
wi th 2,3-di chl oro-5,6-benzoqui ni one (DDQ), i .e., vi a cl eav-
age of the central di mer C-C bond, anal ogous to the TCT
oxi dati on mechani sm shown i n Scheme 1.
Formationof C
10
N
10
, TCBT. I n addi ti on to formati on
of the charge-transfer compl ex [TMPD][TCT], the reac-
ti on of TCT wi th the weak reduci ng agent TMPD l ed
to i sol ati on of a compound of [TMPD][C
10
N
10
] com-
posi ti on i n l ow yi el d (2%). The structure of [TMPD]-
[C
10
N
10
] was determi ned by si ngl e-crystal X-ray di f-
fracti on and reveal s that C
10
N
10
i s the new cyanocar-
bon 4,4,6,6-tetracyano-2,2-bi tri azi ne, TCBT, Fi gure 7.
[TMPD][TCBT] i s val ence ambi guous, because i t can
be formul ated as ei ther [TMPD]
0
[TCBT]
0
, [TMPD]
+
-
[TCBT]
-
, or [TMPD]
2+
[TCBT]
2-
.
As the reducti on i s i rreversi bl e, i t i s possi bl e that a
smal l fracti on of TCT i s reduced and di meri zed to
[TCT]
2
2-
and then forms TCBT through the l oss of two
cyani des. Hence, onl y a smal l amount of TCBT forms,
as observed.
The I R spectrum of TCT of [TMPD][TCBT] has
CN
absorpti ons occurri ng as a three-band pattern (2269,
2254, and 2241 cm
-1
) but i s shi fted sl i ghtl y hi gher i n
energy by 10 cm
-1
wi th respect to TCT. Al so present
for TCBT are absorpti ons at 1342, 1250, and 766 cm
-1
,
whi ch are not present i n the spectrum of [TMPD][TCT].
The resul ti ng compl ex i s di amagneti c and EPR si l ent,
(20) The theory of the ki neti cal l y stabi l i zed product i s suggested on
the basi s of other reported exampl es: (a) Effenberger, F.; Mack, K.
E.; Ni ess, R.; Rei si nger, F.; Stei nbach, A.; Stohrer, W.-D.; Stezowski ,
J. J.; Rommel , I .; Mai er, A. J . Org. Chem. 1988, 53, 4379. (b) Hei nze,
J.; Wi l l mann, C.; Bauerl e, P. Angew. Chem., I nt. Ed. 2001, 40, 2861.
SCHEME 1
FIGURE 7. (a) ORTEP drawi ng (50%) of [TMPD][TCBT] and
(b) vi ew of the offset stacki ng of TMPD and TCBTri ngs, where
TMPD are the l i ghter spheres and TCBT the darker spheres.
Bond l engths for the tri azi ne ri ngs are 1.3333 (15) for C6-
N2, 1.3332 (15) for N2-C7, 1.3335 (16) for C7-N3, 1.3285
(16) for N3-C8, 1.3298 (15) for C8-N4, and 1.3402 (16)
for N4-C6. Bond angl es around the ri ng ni trogens are
113.43, 112.41, and 113.10 (10) for C6-N2-C7, C7-N3-C8,
and C8-N4-C6, respecti vel y, whi l e those around the ri ng
carbons are 126.08, 127.21, and 127.73 (10) for N4-C2-N2,
N2-C7-N3, and N3-C8-N4, respecti vel y.
Del Sesto et al .
3372 J . Org. Chem., Vol. 68, No. 9, 2003
suggesti ng but not concl usi vel y showi ng, as di meri zati on
may occur, that the product i s a charge-transfer compl ex
and not a one-el ectron-transfer sal t, [TMPD]
+
[TCBT]
-
.
The el ectrochemi cal behavi or of [TMPD][TCBT] has a
reversi bl e reducti on of TCBT (TCBT/[TCBT]
-
) at +0.03
V, whi ch i s noti ceabl y di fferent from the reducti on of
TCT, Fi gure 1d. Al so present are the TMPD redox pai rs
of TMPD
0/+
and TMPD
+/2+
at +0.10 and +0.72 V,
respecti vel y.
11
The formul ati on of [TMPD]
0
[TCBT]
0
i s pri nci pal l y
based on the structure of the TMPD mol ecul e as a
functi on of i ts charge. The TMPD ri ng bond l engths are
1.3800 (18) for C1-C1 and 1.4050 (18) for C2-C3
wi thi n the TMPD ri ng, and the C2-N1 bond l ength i s
1.3923 (16) ; these val ues are i n good agreement wi th
the 1.39 reported for TMPD
0
.
21a
I n contrast, for
[TMPD]
+
as the [I
3
]
-
and [Cl O
4
]
-
sal ts, the correspondi ng
bond l engths are 1.362 ( 0.001, 1.426 ( 0.004, and 1.346
( 0.002 .
21b,c
Thus, the i nteratomi c TMPD di stances,
parti cul arl y the C2-N1 di stance, are characteri sti c of
TMPD
0
, not [TMPD]
+
.
The two tri azi ne ri ngs of TCBT i n the TMPD charge-
transfer compl ex are connected by a 1.492 (2) C-C
bond, as expected for a sp
2
-sp
2
si ngl e C-C bond and
observed i n the structure of bi pyri mi di ne, whi ch has a
central C-C bond of 1.498 .
22
Al l of the bond l engths
wi thi n the ri ngs are 1.34 ( 0.01 , and the bond angl es
are 127 and 113 for the N-C-N and C-N-C angl es,
respecti vel y, wi thi n the ri ng, as seen i n most neutral
tri azi ne ri ng systems.
4b
The TMPD and TCBT pl anes
stack al ong chai ns wi th al ternati ng TMPD and TCBT
moi eti es and devi ate from copl anari ty by 1.73, wi th each
TCBT fragment di spl aced from the next TCBT i n the
chai n by a hal f uni t. The pl anes are approxi matel y 3.1
apart, wi th the cl osest contact to the cyano-substi tuted
ri ng carbon of the tri azi ne (C8) bei ng the TMPD ni trogen
(N1) wi th a di stance of 2.903 . The short contact resul ts
i n a sl i ght devi ati on of pl anari ty of the di methyl ami no
group wi th respect to the TMPD central ri ng, as the
ni trogen i s el ectrostati cal l y attracted toward the tri azi ne
ri ng.
2,2-Bi tri azi nes are rare, wi th onl y four other exampl es
previ ousl y reported, 3a-d, i n whi ch the 4- and 6-posi -
ti ons are substi tuted wi th el ectron-donati ng groups.
23
Thi s i s the fi rst structural l y characteri zed bi tri azi ne
reported. The azi de 3d (Y ) N
3
) has been postul ated as
a product i n the decomposi ti on of 2,4,6-tri azi do-1,3,5-
tri azi ne en route to ni trogen-ri ch carbon ni tri de network
sol i ds but has not been i sol ated.
24
However, TCBTcoul d
not be i sol ated from [TMPD][TCBT] by ei ther subl i ma-
ti on or sol vent extracti on, as TMPD and TCBTcosubl i me
and have si mi l ar sol ubi l i ti es. Thi s bi tri azi ne coul d be of
i nterest i n the devel opment of mol ecul e-based magnets
or three-di mensi onal network structures i n general due
to the number of possi bl e coordi nati on si tes for metal s
as wel l as i ts reversi bl e one-el ectron reducti on to the
radi cal ani on.
Formationof [C
10
N
10
]
-
, [TCBT]
-
. Reducti on of TCT
wi th ei ther Cr(mes)
2
, CoCp*
2
, or TDAE, resul ts i n a
second deepl y col ored product i n addi ti on to formati on
of the di mer [TCT]
2
2-
. The sol i d-state EPR spectra of al l
three reducti on products from the reacti on wi th Cr(mes)
2
,
CoCp*
2
, or TDAE i ndi cate the presence of a radi cal , A
-
,
wi th g ) 2.003. Di ssol uti on of any of these products i n
ei ther MeCN or THF al l ows the resol uti on of the EPR
hyperfi ne spl i tti ng pattern due to the coupl i ng of the
radi cal wi th the S ) 1
14
N nucl eus. The observed
spectrum i s i denti cal to that reported for the i n si tu Na
or K reducti on of TCT, and 1
-
was postul ated as the
resul ti ng product.
7
Our room-temperature EPR spectrum
coul d be fi t wi th g ) 2.0035 and wi th a set of two
equi val ent ni trogens wi th
2
A14
N
) 3.347 G, a val ue
characteri sti c of aza ri ng ni trogens,
25
and a set of four
equi val ent ni trogens wi th
4
A
14
N
) 0.765 G and a l i ne
wi dth of 0.240 G, Fi gure 8. These val ues are si mi l ar to
those previ ousl y reported wi th
2
A
14
N
) 3.78 G and
4
A
14
N
) 0.82 G,
7
as evi denced by the di fference spectrum,
Fi gure 8. The 2:4 ni trogen rati o i s i nconsi stent wi th the
structure of [TCT]
-
, whi ch l ed Carri ngton et al . to
propose two possi bi l i ti es: (1) a mol ecul ar rearrangement
to 1
-
, whi ch woul d support a 2:4 rati o, or (2) a Jahn-
Tel l er di storti on of the radi cal ani on of TCT. Al though
reducti on of some al kyl tri azi nes wi th Zn/MeCO
2
H
decompose upon heati ng (through the l oss of NH
3
) to form
tri al kyl i mi dazol es, Scheme 2,
26
anal ogous formati on of
(21) (a) I kemoto, I .; Katgi ri , G.; Ni shi mura, S.; Yakushi , K.; Kuroda,
H. Acta Crystallogr., Sect. B 1979, B35, 2265. (b) de Boer, J. L.; Vos,
A.; Huml , K. Acta Crystallogr. 1968, B24, 542. (c) de Boer, J. L.; Vos,
A. Acta Crystallogr. 1972, B28, 835.
(22) Fernhol t, L.; Rommi ng, C.; Samdal , S. Acta Chem. Scand. Ser.
A 1981, 35, 707.
(23) Ki taji ma, H.; Nakatsuji , A.; Yamauchi , H. Nippon Kagaku
Kaishi 1982, 8, 1425.
(24) Gi l l i an, E. G. Chem. Mater. 2000, 12, 3906.
(25) The symbol x i n
x
A14
N represents the number of equi val ent
ni trogens.
FIGURE 8. EPR si gnal (red) and fi t (bl ue) for [TDAE]
2+
-
{[TCBT]
-
}2 i n THF at room temperature. Fi t was made wi th
2
A
14
N ) 3.347 G and
4
A
14
N ) 0.764 G. The di fference between
the cal cul ated and observed spectra i s i n green at the bottom.
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3373
the fused i mi dazol e 1
-
i s mechani sti cal l y unreasonabl e
due to the number of bonds that need to be broken and
formed.
I t was al so suggested that a di storti on of the structure
of [TCT]
-
, due to breaki ng the degeneracy of two LUMO
orbi tal s of TCTfol l owi ng reducti on, coul d expl ai n the 2:4
ni trogen rati o.
7
Thus, the structure of [TCT]
-
was
computati onal l y i nvesti gated to ascertai n i f a di storti on
occurs and, i f so, the predi cted EPR spectrum. Densi ty
functi onal theory (DFT) cal cul ati ons at the B3LYP l evel
usi ng 6-31+G(2d,2p) basi s sets were carri ed out on the
neutral and radi cal ani on of TCT. The TCT contai ns a
set of degenerate e HOMO orbi tal s and a set of degener-
ate e LUMO orbi tal s, wi th the structural symmetry
bei ng D
3h
. Upon addi ti on of an el ectron to form [TCT]
-
,
the degeneraci es are broken as the symmetry of the
mol ecul e i s reduced to C
2v
. Thus, a Jahn-Tel l er di storti on
i s predi cted upon reducti on, and the resul ti ng SOMO and
cal cul ated spi n densi ty of [TCT]
-
, Fi gure 9b, i ndi cate
that a 2:2:1:1 rati o of i nequi val ent ni trogens usi ng the
atom l abel s i n Tabl e 1 woul d resul t wi th predi cted
hyperfi ne spl i tti ngs of 3.44 (N1,N3), 1.41 (N2), 2.73
(N5,N6), and 0.18 (N4) G, respecti vel y. Hence, al though
a di storti on i s anti ci pated for [TCT]
-
, i ts predi cted EPR
spectrum i s i nconsi stent wi th that observed.
Furthermore, the CV of [TDAE]
2+
[A
-
]
2
does not show
the i rreversi bl e oxi dati on and reducti on characteri sti c of
TCT, but a new, reversi bl e one-el ectron peak at +0.03 V
(vs SCE) appears, Fi gure 1e. Thi s peak at +0.03 V i s
i denti cal to that observed for [TMPD][TCBT]. Li kewi se,
the el emental anal ysi s of the [TDAE]
2+
[A
-
]
2
al so sug-
gests that A
-
i s [TCBT]
-
. Therefore, al though 1
-
i s not
expected on the basi s of the number of bonds that woul d
have to be broken and reformed, the experi mental EPR,
as compared wi th the predi cted spectra, the el emental
anal ysi s, and the di fference i n el ectrochemi cal behavi or
of A
-
, as compared wi th the behavi or of TCTand [TCT]
-
,
suggest that a new speci es i s formed fol l owi ng the
reducti on of TCTand i s [TCBT]
-
. Formati on of [TCBT]
-
can be expected vi a more reasonabl e mechani sti c pro-
cesses as compared to 1
-
(vi de i nfra).
DFT cal cul ati ons of TCBT and [TCBT]
-
were carri ed
out at the B3LYP l evel , and the MO di agram as wel l as
the spi n and charge densi ti es were cal cul ated, Fi gure 10
and Tabl e 1. TCBT contai ns two cl osel y spaced, but not
degenerate, HOMO and HOMO-1 orbi tal s. Upon addi ti on
of an el ectron to form the radi cal ani on, [TCBT]
-
, al l of
the orbi tal s i ncrease i n energy, wi th the two hi ghest fi l l ed
sti l l l yi ng fai rl y cl ose i n energy to one another. The
LUMO orbi tal and spi n densi ty of [TCBT]
-
are predi cted
to be l ocal i zed predomi nantl y wi thi n the ri ngs, wi th a
mi ni mal spi n resi di ng on the ni tri l e ni trogen atoms,
Tabl e 1 and Fi gure 10b. The resul ti ng D
2h
symmetry of
the spi n densi ty woul d propose a set of 2 and a set of 4
equi val ent ni trogens wi thi n the ri ngs and another set of
4 equi val ent ni trogens due to the ni tri l es. Whi l e strong
coupl i ng of the spi n to the two sets of ni trogens wi thi n
the ri ngs are expected, weaker coupl i ng to the ni tri l es i s
al so expected, as there i s very l i ttl e spi n densi ty on the
ni tri l es (<0.003 e
-
). Thi s i s consi stent wi th the observed
EPR spl i tti ngs, wi th a set of 2 and a set of 4 equi val ent
ni trogens wi th strong coupl i ng to the ri ng ni trogens. The
broad peaks (0.24 G l i ne wi dth) i n the spectra obtai ned
coul d be due to the concomi tant weak spl i tti ng of the
peaks from the ni tri l e groups, but the sensi ti vi ty of the
i nstrument does not al l ow thi s very weak coupl i ng (<0.1
G) to be resol ved. I n contrast to the spi n densi ty, the
charge resi des on the ni tri l e and i mi de Ns, Fi gure 10c
and Tabl e 1.
Al l three compounds possessi ng [TCBT]
-
have the
same I R wi th absorpti ons at 1530, 1275, 1180, 950, 915,
and 775 cm
-1
, as wel l as a weak
CN
absorpti on at 2242
cm
-1
. Furthermore, the sol uti on (MeCN) UV/vi si bl e
spectra of the three [TCBT]
-
-contai ni ng compounds have
several i denti cal absorpti ons centered at 18 000 cm
-1
(556 nm), Fi gure 11, i n addi ti on to those attri buted to
the cati on. Thi s l ower-energy absorpti on i s assi gned to
the b
2g
2
b
3u
1
f b
2g
1
b
3u
2
(HOMO-SOMO) transi ti on of the
radi cal ani on, as seen i n the MO di agram for [TCBT]
-
,
Fi gure 10a. Thi s absorpti on i s spl i t i nto fi ve di sti ngui sh-
abl e peaks separated by approxi matel y 1430 cm
-1
, whi ch (26) Cook, A. H.; Jones, D. G. J . Chem. Soc. 1941, 278.
FIGURE 9. (a) Cal cul ated mol ecul ar orbi tal di agram for TCT
o
and [TCT]
-
speci es wi th 90%of the charge pl otted at a contour
of 0.01 e
-
, (b) the spi n densi ty of [TCT]
-
showi ng 95% of the
spi n at a contour of 0.005 e
-
, showi ng sets of equi val ent
ni trogens of 2:2:1:1, and (c) the predi cted charge densi ty for
[TCT]
-
speci es, where red and bl ue represent negati ve (-) and
posi ti ve (+) potenti al s, respecti vel y.
SCHEME 2
Del Sesto et al .
3374 J . Org. Chem., Vol. 68, No. 9, 2003
are attri buted to vi brati onal overtones due to phonon
coupl i ng wi th the exci ted state of the radi cal ani on,
si mi l ar to that noted for [TCNE]
-
.
27
The 1430 cm
-1
spl i tti ngs observed wi thi n the 18 000
cm
-1
(556 nm) absorpti on correspond very cl osel y to the
energy of the ground-state
CdN
absorpti on of 1530 cm
-1
.
The 100 cm
-1
decrease i n frequency i s due a decrease
i n the ri ng CN bond l engths i n the exci ted state, as the
p* orbi tal i s a bondi ng orbi tal for some CdN bonds and
anti bondi ng for the other CdN bonds wi thi n the ri ng,
and the popul ati on of the p* woul d both i ncrease and
decrease CdN bonds, resul ti ng i n a symmetri c (D
2h
)
di storti on of the [TCBT]
-
, wi th l i ttl e change i n the ni tri l e
bonds, as seen i n the change bond l engths cal cul ated i n
Tabl e 2.
The radi cal ani on has a hi gher-energy absorpti on at
29 000 cm
-1
(345 nm), whi ch i s attri buted to the b
3u
1
b
1g
o
f b
3u
o
b
1g
1
transi ti on, whi ch i s consi stent wi th the cal cu-
l ati ons, Fi gure 10a. The b
3u
1
b
ag
o
f b
3u
o
a
g
1
transi ti on i s
i nappropri ate for use i n maki ng thi s assi gnment, because
the ani ons a
g
SOMO + 1 orbi tal i s a vi rtual di ffuse
Rydberg orbi tal that i s more appropri ate to the di ani on
than to the ani on.
The magneti c suscepti bi l i ty, , of the sal ts of the
[TCBT]
-
was determi ned between 2 and 300 K. The
room-temperature-effecti ve magneti c moments,
eff
[) (8T)
1/2
] are 1.72, 2.34, and 2.43
B
for [CoCp*
2
]-
[TCBT]
-
, [Cr(mes)
2
]
+
[TCBT]
-
, and [TDAE]
2+
[[TCBT]
-
]
2
,
respecti vel y. The val ues are consi stent wi th one spi n for
the former compound and two spi ns for the l atter two
compounds as expected. The 2.34
B
moment i s reduced
from the expected 2.45
B
due to the presence of an
i mpuri ty, most l i kel y di amagneti c [TCT]
2
2-
. The (T) can
be model ed as typi cal Curi e-Wei ss behavi or, [T -
]
-1
, and [TDAE]
2+
{]TCBT]
-
}
2
and [Cr(mes)
2
]
+
[TCBT]
-
show weak anti ferromagneti c coupl i ng, wi th ) -3.6
and -0.2 K, respecti vel y. I n contrast, [CoCp*
2
][TCBT]
-
exhi bi ts weak ferromagneti c coupl i ng, wi th ) +3.8 K.
(27) (a) Di xon, D. A.; Mi l l er, J. S. J . Am. Chem. Soc. 1987, 109, 3656.
(b) Mi l l er, J. S.; Krusi c, P. J.; Di xon, D. A.; Rei ff, W. M.; Zhang, J. H.;
Anderson, E. C.; Epstei n, E. J. J . Am. Chem. Soc. 1986, 108, 4459. (c)
Hal l er, I .; Kaufman, F. B. J . Am. Chem. Soc. 1976, 98, 1464.
FIGURE 10. (a) Cal cul ated mol ecul ar orbi tal di agram for
TCBT
o
and [TCBT]
-
speci es wi th 90% of the charge pl otted
at a contour of 0.017 e
-
, (b) the spi n densi ty of [TCBT]
-
showi ng 90%of the spi n at a contour of 0.002 e
-
, showi ng sets
of equi val ent ni trogens of 2:4:4, and (c) the predi cted charge
densi ty for [TCBT]
-
speci es, where red and bl ue represent
negati ve (-) and posi ti ve (+) potenti al s, respecti vel y.
FIGURE 11. Mol ar exti ncti ons of (a) [Cr(mes)2]
+
[TCBT]
-
(dashed l i ne), (b) [CoCp*2]
+
[TCBT]
-
(sol i d l i ne), (c) [TDAE]
2+
-
{[TCBT]
-
}2 (dotted line), and (d) {[Cr(mes)2]
+
}2[TCT]2
2-
(dashed
sol i d l i ne) as sol uti ons i n MeCN. I nset shows the vi brati onal
coupl i ng of [TCBT]
-
.
TABLE 2. Optimized Geometries of Neutral and
Radical Anion of [TCBT]
n
(n ) 0, 1-) fromCalculations
at the Density Functional B3LYP/6-31++G(2d,2p) Level
a
bond
bond l ength ()
n ) 0
bond l ength ()
n ) 1- % change
a 1.506 1.406 -6.6%
b 1.315 1.363 +3.7%
c 1.314 1.295 -1.4%
d 1.316 1.335 +1.4%
e 1.455 1.462 +0.5%
f 1.133 1.136 +0.3%
a
Resul ti ng geometri es for both speci es have D2h symmetry.
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3375
The I R spectrum of [TDAE]
2+
{[TCBT]
-
}
2
i s i denti cal
to the thermol ysi s product i sol ated from TGA/MS experi -
ments of the [TDAE]
2+
[TCT]
2
2-
, i n whi ch the sampl e was
heated unti l the l oss of [CN

] was detected i n the mass

spectrometer. Sol i d [TDAE]
2+
[TCT]
2
2-
was heated to 110
C, si mul ati ng the condi ti ons of the TGA experi ment to
effect the mass l oss of [CN]
x
. A porti on of the sampl e was
removed after 1, 12, and 24 h of heati ng, and i ts I R
spectra were obtai ned, Fi gure 12. The sol i d that remai ned
after 24 h was recrystal l i zed from MeCN. As [TDAE]
2+
-
[TCT]
2
2-
i s heated and decomposes, the i ntensi ty of the
characteri sti c absorpti ons for [TCT]
2
2-
decrease (peaks
l abel ed as ii) whi l e characteri sti c peaks for the [TDAE]
2+
-
{[TCBT]
-
}
2
sampl e i ncreases (peaks l abel ed as i). Thi s
suggests that fol l owi ng formati on [TCT]
2
2-
, l oss of CN

and CN
-
occurs, whi ch resul ts i n the formati on of
[TCBT]
-
, most likely through the intermediate [C
11
N
11
]
2-
,
Scheme 3. The fi nal product of thermol ysi s woul d there-
fore be the two sal ts [TDAE]
2+
{[TCBT]
-
}
2
and [TDAE]
2+
-
[CN
-
]
2
. [TCBT]
-
i s responsi bl e for the 2N:4N EPR si gnal
that i s observed i n both the di rect reducti on of TCTwi th
TDAE, Na, or K and i n the recrystal l i zed thermol ysi s
product of [TCT]
2
2-
. As the decomposi ti on product of
[TCT]
2
2-
i nvol ves the l oss of mass, i t i s l i kel y that [TCT]
-
i s nei ther present nor the speci es responsi bl e for the
observed EPR spectra.
Ti me-resol ved, stopped-fl ow I R studi es were performed
on the reacti on mi xture, wi th the fi rst spectra begi nni ng
at 50 ms fol l owi ng mi xi ng, and recorded approxi matel y
every 15 s over the course of 11 mi n, Fi gure 13a. The
fi rst scan shows the presence of a l arge peak at 1670
cm
-1
, characteri sti c of the [TDAE]
2+
,
28
i ndi cati ng that the
el ectron transfer from TDAE to TCT occurs i n l ess than
20 ms, the detecti on l i mi t of the system. Addi ti onal l y,
peaks characteri sti c of both [TCT]
2
2-
and [TCBT]
-
are
al so present i mmedi atel y, suggesti ng that di meri zati on
and the i ni ti ati on of decomposi ti on to [TCBT]
-
al so
requi re <20 ms. Thi s suggests that the i ntermedi ate i n
the transformati on has characteri sti cs of both [TCT]
2
2-
and [TCBT]
-
, whi ch coul d possi bl y be [C
11
N
11
]
2-
. Thi s
i s al so consi stent wi th the el ectrochemi cal behavi or of
TCT bei ng i rreversi bl e at even the greatest scan rates
studi ed (2000 mV/s). Moni tori ng of the peaks character-
i sti c of [TCT]
2
2-
, at 1590 and 1330 cm
-1
, as a functi on of
ti me shows the gradual decrease i n i ntensi ty, al ong wi th
the si mul taneous i ncrease of i ntensi ty of the character-
i sti c peaks of [TCBT]
-
at 1530 and 950 cm
-1
, Fi gure 13b.
Hence, the decomposi ti on of [TCT]
2
2-
to [TCBT]
-
occurs
i n a mul ti step process, as seen i n the change i n sl opes i n
Fi gure 13b duri ng the experi ment. However, the ki neti cs
i s not wel l understood and sti l l under i nvesti gati on.
Nonethel ess, i t i s apparent that the reducti on of TCT
resul ts i n a very rapi d di meri zati on fol l owed by a sl ower
decomposi ti on to form the new radi cal ani on [TCBT]
-
.
[Cr(mes)
2
]
+
[TCBT]
-
and [CoCp*
2
]
+
[TCBT]
-
di spl ay
the same EPR spl i tti ngs, as wel l as an I R si mi l ar pattern
to that of [TDAE]
2+
{[TCBT]
-
}
2
. However, pure sampl es
of [Cr(mes)
2
]
+
[TCBT]
-
coul d not be obtai ned, as i t
cocrystal l i zes from sol uti on wi th the respecti ve sal t of
[TCT]
2
2-
. Thermol ysi s experi ments, si mi l ar to that of the
[TDAE]
2+
sal t decomposes [TCT]
2
2-
formi ng sal ts of
[TCBT]
-
, coul d not be carri ed out on the [Cr(mes)
2
]
+
-
[TCBT]
-
and [CoCp*
2
]
+
[TCBT]
-
due to the decomposi -
ti on of the cati ons upon heati ng to temperatures suf-
fi ci ent to effect the l oss of [CN]
x
from [TCT]
2
2-
.
Mechanistic Considerations. Several feasi bl e mech-
ani sms for the formati on of TCBTand [TCBT]
-
from the
reducti on of TCT are shown i n Scheme 3. The most
feasi bl e of these i s Scheme 3a, whi ch goes through the
di mer di ani on i ntermedi ate [TCT]
2
2-
, whi ch has been
i sol ated from the di rect reducti on of TCT and, as di s-
cussed, decomposes to form [TCBT]
-
on the basi s of
thermol ysi s and spectroscopi c data. When heated or
al l owed to stand for extended peri ods of ti me (1 day or
l onger), [TCT]
2
2-
can l ose CN

, whi ch evol ves as C

2
N
2
,
both of whi ch are seen i n the mass spectra (MS) duri ng
the TGA/MS experi ments as they are evol ved from the
sol i d sal ts of [TCT]
2
2-
. Thi s resul ts i n the formati on of
[C
11
N
11
]
2-
, whi ch coul d l ose CN
-
i n sol uti on to yi el d
[TCBT]
-
. I n the thermol ysi s of sol i d [TDAE]
2+
[TCT]
2
2-
,
the presence of [TCT]
2
2-
i s evi dent i n the I R of the sampl e
unti l the thermol ysi s product i s recrystallized, suggesti ng
that the di ssol uti on i s requi red to l ose a charged speci es
such as CN
-
, ul ti matel y yi el di ng [TCBT]
-
. The sol uti on-
phase, ti me-resol ved I R spectra al so i ndi cate the presence
of both [TCT]
2
2-
and [TCBT]
-
after the i ni ti al reducti on,
Fi gure 13, and the ensui ng si mul taneous decomposi ti on
of [TCT]
2
2-
and formati on of [TCBT]
-
al so support thi s
mechani sm.
Scheme 3, whi ch goes through i ntermedi ate [TCT]
2
-
,
i s al so feasi bl e. As TMPD i s a weak donor and onl y
reduces 0.01% of TCT, i t i s extremel y unl i kel y for two
[TCT]
-
to react together i n the reacti on mi xture to
eventual l y yi el d TCBT. I n contrast, [TCT]
-
may react
(28) Pokhodni a, K. I .; Papavassi l ou, J.; Umek, P.; Omerzu, A.;
Mi hai l ovi c, D. J . Chem. Phys. 1999, 110, 3606.
FIGURE 12. I R spectra of (a) [TDAE]
2+
{[TCBT]
-
}2, (b)
[TDAE]
2+
[TCT]2
2
, and [TDAE]
2+
[TCT]2
2-
thermol yzed for (c)
1, (d) 12, and (e) 24 h and (f) recrystal l i zed after 24 h, as KBr
pel l ets. Peaks l abel ed i are characteri sti c peaks for [TCBT]
-
,
and those l abel ed ii are characteri sti c for [TCT]2
2-
.
Del Sesto et al .
3376 J . Org. Chem., Vol. 68, No. 9, 2003
wi th neutral TCT to form [TCT]
2
-
. However, the el ec-
trochemi cal behavi or of [TCT]
2
-
shows that i t i s unstabl e,
as evi denced by the i rreversi bl e oxi dati on of [TCT]
2
2-
i n
the di fferent sal ts produced, e.g., Fi gure 1d. Thi s i r-
reversi bi l i ty coul d be due to [TCT]
2
-
decomposi ng to form
ei ther [TCBT]
-
or [TCT]
-
and TCT
0
, Scheme 1.
The l oss of two CN
-
fragments si mul taneousl y from
the i ntermedi ate [TCT]
2
2-
and formati on TCBT, Scheme
3b, are possi bl e. Thi s, however, i s unl i kel y, as CN
-
shoul d
not si mpl y be el i mi nated from the sal ts i n the sol i d state
as seen i n the thermol ysi s experi ments. Al so, i f two [CN]
-
fragments are l ost, the resul t woul d be a [cati on]
+
[CN]
-
sal t and TCBT
0
i n sol uti on. The ori gi nal reduci ng agents
woul d then exi st as cati ons i n i on pai rs wi th the cyani de
ani ons, and there woul d be l i ttl e, i f any, reduci ng agent
l eft to reduce the resul ti ng neutral TCBT to i ts radi cal
ani on. As the yi el ds of the el ectron-transfer reacti ons
wi th TDAE, Co
I I
Cp*
2
, and Cr
0
(mes)
2
are si gni fi cant
(g20%), thi s mechani sm i s not probabl e.
Conclusion
The radi cal ani on of TCT, [TCT]
-
, i s unstabl e i n
sol uti on as seen i n the el ectrochemi cal experi ments, as
wel l as by the i sol ati on of [TCT]
2
2-
. Reacti on of TCTwi th
strong el ectron donors resul ts i n an el ectron-transfer
produci ng the unstabl e [TCT]
-
, whi ch then di meri zes as
sal ts of [TCT]
2
2-
. I nstabi l i ty of tri cyanoarenes i s al so seen
i n the reducti on of TCB to form [TCB]
2
2-
, whi ch di meri zes
at the unsubsti tuted carbon of the benzene ri ng, as
opposed to the ni tri l e-substi tuted carbon as previ ousl y
predi cted and as observed for [TCT]
2
2-
.
Reacti on of TCT wi th weak el ectron donors such as
TMPD and TTF resul ts i n charge-transfer compl exes of
TCT, whi ch i n the presence of trace water, undergoes
nucl eophi l i c substi tuti on to form DCTOH, whi ch i n the
presence of a suffi ci entl y strong base such as TMPD
undergoes an aci d-base reacti on formi ng [DCTO]
-
.
Decomposi ti on of [TCT]
2
2-
i n the sol i d state or sol uti on
ul ti matel y produces the radi cal ani on of [TCBT]
-
; the
neutral speci es of whi ch was i sol ated and structural l y
characteri zed from the reacti on of TCT wi th TMPD.
Mechani sti c anal ysi s suggests that the i rreversi bl e re-
ducti on of TCT occurs vi a di meri zati on of [TCT]
-
to
[TCT]
2
2-
, whi ch then decomposes to [TCBT]
-
and, hence,
i s responsi bl e for the previ ousl y mysteri ous 2:4 ni trogen
rati o observed i n the EPR spectrum. The l ow charge and
spi n densi ti es on the termi nal ni tri l es suggest that TCBT
and [TCBT]
-
wi l l be poor l i gands as wel l as poor spi n-
coupl i ng l i nkages, and thei r use i s unl i kel y to l ead to new
mol ecul e-based magnets. However, i f metal coordi nati on
of the ri ng ni trogens i n [TCBT]
-
occurs, as observed for
bi pyri di ne- and bi pyri mi di ne-contai ni ng structures, anal o-
gous bui l di ng of network structures may occur wi th the
possi bi l i ty of magneti c exchange through the spi n-beari ng
[TCBT]
-
l i gand.
Experimental Section
Al l reacti ons were carri ed out i n a drybox under ni trogen.
Al l sol vents were dri ed by di sti l l ati on under ni trogen over
CaH2 or Na/benzophenone, and al l reagents were used as
commerci al l y avai l abl e materi al s.
Sampl es for I R spectra were prepared as KBr pressed
pel l ets. Ti me-resol ved i nfrared spectra were obtai ned wi th a
SCHEME 3
FIGURE 13. Ti me dependence of I R absorpti ons at 1530, 950,
1590, and 1330 cm
-1
for the reacti on of TDAE and TCT i n
MeCN usi ng a stopped-fl ow reacti on mi xer. Peaks at 1530 and
950 cm
-1
are characteri sti c of [TCBT]
-
, and the peaks at 1590
and 1330 cm
-1
are characteri sti c of [TCT]2
2-
.
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3377
rapi d-mi xi ng stopped-fl ow attachment constructed i n-house.
The devi ce i s centered around on i ntegrated mi xer-fl ow cel l
based on a mi croCI RCLE ATR accessory and empl oyed a ZnSe
ATR crystal . The effecti ve path l ength i n thi s confi gurati on i s
13 m. Spectra were col l ected wi th a Bruker I FS 66/s spec-
trometer i n rapi d-scan mode wi th a resol uti on of 8 cm
-1
.
29
Sol i d-state UV/vi si bl e spectra were performed on KBr pel l ets
of the respecti ve sampl es (2% w/w sampl e/KBr).
Cycl i c vol tammograms were performed scanni ng from +1.5
to -2.0 V wi th scan rates of 2-5000 mV/s, wi th the reported
CVs at 100 mV/s. Pt worki ng and counter el ectrodes were used
wi th a Ag/AgCl reference el ectrode charged wi th [Me4N]Cl , and
[NMe4]Cl was used as a supporti ng el ectrol yte i n acetoni tri l e
(0.10 M). Al l CVs were referenced to a ferrocene/ferroceni um
standard and reported vs SCE.
Thermal properti es and mass spectrometry were performed
wi th a thermogravi metri c anal yzer (TGA), wi th the gas outl et
connected to a mass spectrometer wi th an i oni zati on potenti al
of 70 eV. El emental anal ysi s was performed by Compl ete
Anal ysi s Laboraotri es, I nc. (Parsi ppany, NJ).
Magneti c suscepti bi l i ty measurements were performed be-
tween 2 and 300 K at a fi el d of 1000 Oe on a SQUI D
magnetometer as previ ousl y descri bed.
30
EPR spectra were
recorded usi ng an X-band spectrometer wi th 1,1-di phenyl -2-
pi cryl hydrazyl (DPPH) as an external standard (g) 2.0036).
31
Computati onal studi es were performed at the DFT B3LYP
l evel usi ng 6-31+G(2d,2p) basi s sets and usi ng RHF theory
for the [DCTO]
-
and neutral mol ecul es and UHF for the
radi cal ani ons. Vi sual i zati on of the mol ecul ar orbi tal s and spi n
densi ti es were created wi th MOLDEN for the TCBT speci es
and an i n-house versi on of MOLEKEL for the TCBT speci es.
X-ray di ffracti on studi es were performed on a CCD di ffrac-
tometer equi pped wi th Mo KR ( ) 0.71073 ) radi ati on. Al l
structures were sol ved by di rect methods usi ng the program
SI R-97 and refi ned by the ful l -matri x l east-squares method
on F
2
wi th SHELXL 97.
32a
Ani sotropi c thermal parameters
were assi gned to al l atoms, except that the hydrogen atoms
and thei r posi ti ons were assi gned usi ng the ri di ng model .
ORTEP di agrams were generated usi ng ORTEP 3.
32b
1,3,5-Tri cyanobenzene, TCB,
33
was prepared usi ng l i terature
methods.
2,4,6-Tricyano-1,3,5-triazine, TCT. The synthesi s of TCT
i s based upon a patent.
34
Sol i d KCN (15 g, 0.31 mol ) was added
to a suspensi on of cyanuri c chl ori de (2,4,6-tri chl oro-1,3,5-
tri azi ne; 17 g, 0.07 mol ) i n 250 mL of dry MeCN whi l e sti rri ng
vi gorousl y at room temperature. The mi xture was al l owed to
sti r for 40 h, over whi ch ti me the mi xture turned a bri ck-red
col or. The resul ti ng KCl and unreacted KCN were fi l tered and
destroyed i n a bl each bath. The sol vent of the brown fi l trate
was removed under reduced pressure, and the oi l y resi due was
sti rred wi th 100 mL of CH
2Cl 2 for 12 h to extract the crude
TCT. The i nsol ubl e materi al was fi l tered out and washed twi ce
more wi th 100 mL of CH
2Cl 2. The sol vent of the combi ned
fi l trates was agai n removed under reduced pressure, yi el di ng
a l i ght brown powder of crude TCT, whi ch was puri fi ed by
subl i mati on at 110 C at 5 mTorr of pressure wi th an
acetone/CO
2 condenser to gi ve whi te pr i smati c cr ystal s.
Yi el d: 5.7 g (52%). Mp: 119-121 C. I R, , cm
-1
: 2301 w, 2277
m, 2252 s, 2063 vw, 1652 m, 1550 m, 1510 s, 1336 s, 938 s,
822 s, 520 s, 422 s. MS, m/z (rel %): 52 (39.8), 78 (5.7), 104
(100.0), 156 (M
+
; 58.6).
[TTF][TCT]. A sol uti on of TTF (200 mg, 0.98 mmol ) i n 10
mL of MeCN was added to a sol uti on of TCT (152 mg, 0.98
mmol ) i n 5 mL of MeCN. The sol uti on turned an i mmedi ate
deep-green col or and was al l owed to sti r for 12 h. The sol vent
was evaporated and the resi due recrystal l i zed from hot MeCN,
yi el di ng a bl ue-green powder. I R, , cm
-1
: 3100 w, 3068 w,
2262 w, 2241 m, 1504 s, 1482 s, 1328 m, 1320 m, 1249 w, 1082
w, 971 w, 936 m, 796 s, 782 m, 733 w, 673 m, 659 m, 516 m.
Anal . Cal cd for C
12H4N6S4: C, 39.98; H, 1.12; N, 23.31.
Found: C, 40.15; H, 1.29; N, 22.30. Crystal data for [TTF]-
[TCT]: C
12H4N6S4, M ) 360.45, orthorhombi c, space group
Pbca, a ) 7.1430(1) , b ) 16.5138(5) , c ) 25.4640(7) , V
) 3003.68(13)
3
, Z ) 8, Fcal cd ) 1.594 Mg/m
3
, absorpti on
coeffi ci ent ) 0.636 mm
-1
, F(000) ) 1456, refl ecti ons col l ected
6305, i ndependent refl ecti ons ) 3416 [R(i nt) ) 0.0378], GOF
) 1.038, R ) 0.0609, wR2 ) 0.0951. CCDC-172417.
[TMPD][TCT]. A sol uti on of TMPD (100 mg, 0.61 mmol )
i n 5 mL of MeCN was added to a sol uti on of TCT(95 mg, 0.61
mmol ) i n 5 mL of MeCN. A bl ue powder i mmedi atel y preci pi -
tated, whi ch was recrystal l i zed from hot MeCN. I R, , cm
-1
:
2957 m, 2891 m, 2851 m, 2806 m, 2256 m, 2246 m, 2235 m,
1610 m, 1521 s, 1497 s, 1479 s, 1330 m, 1317 m, 1213 m, 1178
w, 1130 w, 1056 w, 970 w, 946 m, 829 m, 807 w, 796 s, 660 m,
542 w. Anal . Cal cd for C
16H16N8: C, 59.99; H, 5.03; N, 34.98.
Found: C, 59.97; H, 5.08; N, 34.90.
[HTMPD]
+
[DCTO]
-
. The above procedure was fol l owed
exactl y, wi th 0.5 mL of H2O added to the TCT sol uti on before
addi ti on of the TMPD, resul ti ng i n an i mmedi ate yel l ow
preci pi tate. I R, , cm
-1
: 2960 w, 2904 w, 2860 w, 2819 w, 2249
w, 2224 w, 1580 s, 1540 s, 1523 s, 1446 s, 1361 m, 1309 s,
1235 w, 1186 s, 1055 m, 997 w, 934 m, 910 w, 815 s, 668 w,
547 m. Anal . Cal cd for C
15H17N7O: C, 57.87; H, 5.50; N, 31.49.
Found: C, 57.87; H, 5.44; N, 31.56. Crystal data for [HTMPD]
+
-
[DCTO]
-
: C15H17N7O, M ) 311.36, monocl i ni c, space group
P21/m, a ) 10.641(3) , b ) 6.614(3) , c ) 11.793(5) , )
90.07(3), V ) 830.0(2)
3
, Z ) 2, Fcal cd ) 1.246 Mg/m
3
,
absorpti on coeffi ci ent ) 0.085 mm
-1
, F (000) ) 328, refl ecti ons
col l ected ) 6184, i ndependent refl ecti ons ) 2210 [R(i nt) )
0.0660], GOF ) 0.873, R ) 0.0431, wR2 ) 0.1054. CCDC-
172418.
Reduction of TCT with Cr(mes)2 in MeCN. A sol uti on
of bi s(mesi tyl ene)chromi um(0) (100 mg, 0.34 mmol ) i n 15 mL
of MeCN was added to TCT (53 mg, 0.34 mmol ) i n 5 mL of
MeCN. A purpl e i nsol ubl e materi al formed and was fi l tered
out and i denti fi ed as [Cr(mes)
2]
+
[TCBT]
-
(yi el d ) 44 mg
(28%)) by compari son of the I R, UV-vi s, and EPR spectra wi th
those of [CoCp*2]
+
[TCBT]
-
and [TDAE]
2+
{[TCBT]
-
}2. I R, ,
cm
-1
: ([TCBT]
-
) 2242 vw, 1532 vs, 1274 s, 1179 m, 951 vs,
908 m, 773 m; ([Cr(mes)2]
+
) 1446 s, 1377 md, 1032 m, 977 m,
440 m. EPR: g[TCBT]
-
) 2.0034,
2
A14N ) 3.346 G,
4
A14N ) 0.767
G (THF, MeCN); gCr
I
) 1.9872.
The sol vent of the fi l trate was al l owed to sl owl y evaporate,
resul ti ng i n l arge orange crystal s, and determi ned to be
{[Cr(mes)2]
+
}2[TCT]2
2-
by si ngl e-crystal X-ray di ffracti on.
Yi el d: 94 mg (61%). I R, , cm
-1
: ([TCT]2
2-
) 2237 vw, 1590 s,
1326 vs, 910 w; (Cr(mes)2
+
) 1452 m, 1387 m, 1033 m, 1001 w.
EPR: gCr
I
) 1.9873. Crystal data for {[Cr(mes)2]
+
}2[TCT]2
2-

2MeCN: CCDC-163649.
Reduction of TCT with CoCp*2 and TDAE in MeCN.
A sol uti on of the reduci ng agent (0.30 mmol ) i n 10 mL of MeCN
was added to TCT (47 mg, 0.30 mmol ) i n 5 mL of MeCN
resul ti ng i n a purpl e sol uti on. The sol vent was al l owed to
sl owl y evaporate to hal f the ori gi nal vol ume and then cool ed
to 0 C, al l owi ng a purpl e preci pi tate to form that was
subsequentl y fi l tered and col l ected. Crystal s sui tabl e for si ngl e-
crystal X-ray di ffracti on studi es coul d not be i sol ated.
[CoCp*
2]
+
[TCBT]
-
. Yi el d: 6 mg (4%). I R, , cm
-1
:
([TCBT]
-
) 2243 vw, 1530 vs, 1275 s, 1179 m, 951 vs, 910 m,
775 m; ([CoCp*2]
+
) 1460 m, 1375 s, 1017 s. EPR: g[TCBT]
)
2.0032,
2
A14N ) 3.347 G,
4
A14N ) 0.764 G (THF, MeCN). Anal .
(29) Dunn, B. C.; Marda, J. R.; Eyri ng, E. M. Appl. Spectrosc. 2002,
55, 751.
(30) Brandon, E. J.; Ri ttenberg, D. K.; Ari f, A. M.; Mi l l er, J. S. I norg.
Chem. 1998, 37, 3376.
(31) Al tschul er, S. A.; Kozyrev, B. M. I n Electron Paramagnetic
Resonance; Pool e, C. P., Jr., Ed.; Academi c Press: New York, 1964; p
298.
(32) (a) Shel dri ck, G. M. SHELX97-2: Programfor Crystal Structure
Analysis(Release97-2); Uni versi tat of Gotti ngen: Gotti ngen, Germany,
1998. (b) Farrugi a, L. J. J . Appl. Crystallogr. 1997, 30, 565.
(33) Hi l l , M.; Mahon, M. F.; Mol l oy, K. C. J . Chem. Soc., Dalton
Trans. 1996, 1857.
(34) Beck, G.; U.S. Patent 5,086,172, 1992.
Del Sesto et al .
3378 J . Org. Chem., Vol. 68, No. 9, 2003
Cal cd for C30H30N10Co: C, 61.12; H, 5.13; N, 23.76. Found: C,
60.96; H, 5.01; N, 23.79. Crystal s sui tabl e for si ngl e-crystal
X-ray di ffracti on studi es coul d not be i sol ated.
[TDAE]
2+
{[TCBT]
-
]2. Yi el d: 670 mg (37%). I R, , cm
-1
:
([TCBT]
-
) 2242 vw, 1528 vs, 1275 s, 1179 m, 950 vs, 908 m,
772 m; ([TDAE]
2+
) 1670 s, 1659 s, 1420 s, 1042 w, 865 w, 680
w.
26
EPR: g[TCBT]
) 2.0039,
2
A14N ) 3.347 G,
4
A14N ) 0.765 G
(THF, MeCN). Anal . Cal cd for C30H24N24: C, 50.01; H, 3.33;
N, 46.70. Found: C, 49.89; H, 3.55; N, 46.58.
Reducti on of the vol ume of the fi l trate fol l owed by l ayeri ng
of the fi l trate wi th hexanes resul ted i n a bei ge-col ored pre-
ci pi tate, determi ned to be sal ts of [TCT]2
2-
.
{[CoCp*2]
+
}2[TCT]2
2-
. Yi el d: 10 mg (7%). I R, , cm
-1
:
([TCT]2
2-
) 2237 vw, 1587 s, 1326 vs, 914 w; ([CoCp*2]
+
) 1471
m, 1382 m, 1024 m. Anal . Cal cd for Co2C52H60N12: C, 64.30;
H, 6.23; N, 17.32. Found: C, 64.14; H, 6.28; N, 17.04.
[TDAE]
2+
[TCT]2
2-
. Yi el d: 210 mg (21%). I R, , cm
-1
:
([TCT]2
2-
) 2237 vw, 1592 s, 1328 vs, 906 w; ([TDAE]
2+
) 1668
s, 1655 s, 1402 m, 1047 w, 863 w. Anal . Cal cd for C22H24N16:
C, 51.55; H, 4.72; N, 43.73. Found: C, 51.38; H, 4.67; N, 43.84.
[TMPD][TCBT]. Si mi l ar reacti on condi ti ons were used for
the reducti on of TCT wi th CoCp*2 and TDAE i n MeCN i n a
1:1 stoi chi ometri c rati o. The resul ti ng sol uti on was l eft for 2
weeks and the sol vent al l owed to sl owl y evaporate, resul ti ng
i n deep bl ue-col ored pri smati c crystal s. Yi el d: 4 mg; 2.1%. I R,
, cm
-1
: 2957 m, 2891 m, 2851 m, 2806 m, 2269 vw, 2254 w,
2241 m, 1520 s, 1498 s, 1446 m, 1406 m, 1343 s, 1322 s, 1248
m, 1219 m, 1176 m, 1121 w, 1055 m, 977 w, 949 m, 929 m,
824 m, 805 s, 765 m, 681 w, 658 m, 538 w, 515 w. Crystal
data for [TMPD][TCBT]: C
10H8N6, M ) 212.22, monocl i ni c,
space group P21/a, a ) 7.3864(3) , b ) 15.0865(3) , c )
9.4932(4) , ) 95.2112(14), V ) 1053.50(6)
3
, Z ) 4, Fcal cd
) 1.338 Mg/m
3
, absorpti on coeffi ci ent ) 0.090 mm
-1
, F (000)
) 440, refl ecti ons col l ected ) 4380, i ndependent refl ecti ons )
2381 [R(i nt) ) 0.0237], GOF ) 1.050, R ) 0.0406, wR2 )
0.0990. CCDC-178429.
Acknowledgment. The authors grateful l y acknowl -
edge the support from the NSF (Grant CHE9320478)
and the DOE (Grant DE FG 03-93ER45504). R.E.D.S
and J.S.M appreci ate the el ectrochemi cal assi stance
from Kyl e Grant, John Watki ns, and Henry Whi te.
R.E.D.S. al so thanks the Uni versi ty of Utah Graduate
School for a research fel l owshi p. J.J.N. thanks Mi ni s-
teri o de Ci enci a y Tecnol ogi a and CI RI T(Project PB98-
1166-C02-02 and 2001-SGR-00044). We thank Mi chael
A. Stecker, MD, for permi ssi on to use hi s photograph
for the front cover i l l ustrati on.
Supporting Information Available: X-ray CI F fi l es
for [TTF][TCT], [HTMPD]
+
[DCTO]
-
, {[Cr(mes)2]
+
}2[TCT]2
2-

2MeCN, and [TMPD][TCBT] (these fi l es have al so been

deposi ted wi th the Cambri dge Crystal l ographi c Data Centre,
ref nos. CCDC-172417, CCDC-172418, CCDC-163649, and
CCDC-178429, respecti vel y) and computati onal data for 1,3,5-
tri cyanotri azi ne, the 1,3,5-tri cyanotri azi ne ani on, the 1,3,5-
tri cyanotri azi ne di ani on, 4,4,6,6-tetracyano-2,2-bi tri azi ne, the
4,4,6,6-tetracyano-2,2-bi tri azi ne ani on, and the 2,4-di cyano-
6-hydroxy-s-tri azi ne ani on, [DCTO]
-
. Thi s materi al i s avai l abl e
free of charge vi a the I nternet at http://pubs.acs.org.
JO025833H
Formation of Novel 4,4,6,6-Tetracyano-2,2-bitriazine
J . Org. Chem, Vol. 68, No. 9, 2003 3379