Chem 59-651 Non-Existent Compounds

and Ways to Make Them!

A variety of compounds were classified in a 1965 book by W. E.
Dasent as being non-existent in that arguments could be made
that such compounds were unlikely ever to be made. This was
meant as more as a teaching tool (he realized that there may be
ways to overcome the inherent instability of the compounds he
described) and it is instructive to examine the types of
arguments that he used, which include:

- Electron Configuration

- Thermodynamic Stability

- Kinetic Stability

- Orbital overlap

- Electronegativity differences
Chem 59-651 NX5 vs. PX5
While the compounds PX5 are stable known compounds for X=
F, Cl, Br and maybe even I, the analogous N compounds are not
known. The standard explanation regarding the instability of the
NX5 species is that such compounds would violate the octet
rule and must be impossible because N does not have access to
low-energy d orbitals.

2s22p3 2s12p33d1 ca. 18.9 eV 1 eV = 96.49 kJ/mol

1 cal = 4.184 J
3s23p3 3s13p33d1 ca. 14.4 eV

While this may seem reasonable, is the octet rule truly valid even
for the second row elements? Are d orbitals necessary at all?
Remember the alternative description of the bonding in PF5:
Chem 59-651 What about NF5
Since F is the most electronegative of the elements and the
smallest of the halides, it was the best candidate to make an NX5
compound.

K. O. Christie was able to make the first [NF4]+ salt in 1966 (Inorg.
Nucl. Chem. Lett., 1966, 2, 83.) and Born-Haber cycle calculations
revealed that [NF4][F] should have around the same energy as
NF5. In 1992, Christie et al. (JACS, 1992, 114, 9934) obtained the
following result:

[NF4][BF4] + [NMe4][F] [NMe4][BF4] + NF3 + F2

To date, all attempts to make NF5 have failed and ab initio and density
functional theory calculations (H. F. Schaefer, JACS, 1998, 120, 11439)
suggest that it may be metastable, at best. The energy of the
disproportionation reaction is exothermic by about 42 kcal/mol.
NF5 NF3 + F2
 Chem 59-651 The Instability of NF5
Furthermore, radiotracer studies using 18F have not shown even
the transient existence of NF5.

The instability of compounds such as NF5 is probably best

understood in the context of size and electronegativity. The N-F
bonds in the caculated D3h structure for NF5 are 1.381
(equatorial) and 1.608 (axial). This means that there would be F
atom contacts of around 2.12 between the axial and equatorial F
atoms; the van der Waals radius of F is 1.47 . In PF5 the
distances are 1.608 (axial) and 1.570 (equatorial).

Perhaps more importantly, N is almost as electronegative as F so

there is very little polarity to strengthen the N-F bonds, whereas the
difference in electronegativity between F and P produces very
polarized bonds.
Questions to ponder: If size and polarity are the only important
factors, could we not make NH5? What is the nature of the
bonding in the molecule we usually use as an ionization source in
chemical ionization mass spectrometry, CH5+? (See: G. A. Olah, Acc.
Chem. Res., 1997, 30, 245) [C(AuPPh3)5]+
 Chem 59-651 CCl4 vs SiCl4
Some of the compounds that Dasent discussed are more surprising for their
stability. For example, carbon tetrachloride is remarkbly stable in water or
alcohols when one considers the bond energies involved. CCl4 should react
with water to form CO2 and H-Cl in a very exothermic reaction. The heavier
congener of carbon tetrachloride, SiCl4 reacts with water readily.
C=O H-O
800 460

C-Cl H-Cl
328 428

Si-Cl Si-O
381 452 CCl4
SiCl4
These energies are in kJ/mol
The reason for the relative stability of carbon tetrachloride is the small size of carbon,
which is completely surrounded by the Cl atoms. This situation does not allow for the
convenient approach of the nucleophilic hydroxy group and the small size of C means
that it would be impossible to form the required 5-coordinate intermediate thus carbon
tetrachloride kinetically stable. Similar arguments can be used to explain the
hydrolysis of SF4 versus the stability of SF6 (which should react more exothermically).
 Chem 59-651 PCl5 and SbCl5 vs. AsCl5

Perhaps one of the more surprising of Dasents non-existent compounds

is AsCl5, because PCl5 and SbCl5 are both stable compounds.

The relative instability of AsCl5 is related to its position in the periodic table
and is explained by the relative stability of the As(III) oxidation state
versus that of the As(V) oxidation state. This stability is a manifestation of
the d-block contraction that also affects Ga and Ge.

AsCl5 AsCl3 + Cl2

The disproportionation of
arsenic pentachloride to the
trichloride and chlorine is
rendered favourable by the
higher energy required to use
the lone pair electrons on As
(either for hybridization or
planarization).
 Chem 59-651 AsF5 vs. AsCl5
The relative instability of AsCl5 may also seem surprising because AsF5 is
a stable compound.

It would seem that in this case one cannot make arguments based on the relative
energies of the As(III) oxidation state versus that of the As(V) oxidation state.
While this is debatable, a better answer is perhaps found in the examination of
bond energies and the overall reaction energy that we might expect using
equations similar to a Born-Haber cycle:
AsX3(l) AsX3(g) H1
As-Cl As-F
321 406 X2(g) 2 X (g) H2
Cl-Cl F-F
240 155 AsX3(g) + 2 X(g) AsX5(g) H3

The energies listed in

books (kJ/mol values AsX5(g) AsX5(l) H4
taken from Huheey, Assuming that H1 and H4 cancel each other, this still predicts that
Keiter and Keiter, 1993) AsCl5 should be viable, however to a much smaller extent than AsF5.
are not always helpful. One must be cautious of using such mean bond energies:
E.g. As(III)-F 484; experimentally the formation of PCl5 from PCl3 and Cl2 suggests that
As(V)-F 406. the enthalpy for the last two P-Cl bonds is only 168 kJ/mol not the
326 kJ/mol listed in books.
 Chem 59-651 The synthesis and structure of AsCl5

AsCl5 was eventually synthesized

photochemically at low
temperature by K. Seppelt (Angew.
Chem., Int. Ed. Engl., 1976, 15, 377)
and the structure of the molecule
was recently reported (Z. Anorg.
Allg. Chem., 2002, 628, 729). It is a
metastable and highly reactive
compound.
 Chem 59-651 Homonuclear Single Bond Strengths

H-H These energies are in

kJ/mol and are very
432
approximate but the
trends are useful (all
Li-Li Be-Be B-B C-C N-N O-O F-F
values taken from N. C.
105 (208) 293 346 167 142 155 Norman, 1997 and
Huheey, Keiter and
Na-Na Mg-Mg Al-Al Si-Si P-P S-S Cl-Cl Keiter, 1993).
72 (129) n/a 222 201 226 240

K-K Ca-Ca Ga-Ga Ge-Ge As-As Se-Se Br-Br

49 (105) 115 188 146 172 190

Rb-Rb Sr-Sr In-In Sn-Sn Sb-Sb Te-Te I-I

45 (84) 100 146 121 (126) 149

The general trend is for bonds to weaken down a given group because of
larger internuclear distances and less effective orbital overlap. Note the
anomalies, in particular, the weakness of the N-N, O-O and F-F single
bonds! These anomalies are caused by lone pair electron repulsion.
 Chem 59-651 Isodesmic Equations
One of the most convenient methods that one can use to assess the
relative stability of valence isomers is the application of isodesmic
equations. Isodesmic means that there are the same number of bonds
on each side of the equation and the assumption is that the energies of
the bonds are the only important quantity in determining the
thermodynamic preference of the reactions.

For example, isodesmic reactions can be used to determine the stability of

different possible allotropes:
N
N
2 N N N
N

2 * 940 kJ/mol 6 * 160 kJ/mol

= 1880 kJ/mol = 960 kJ/mol

Thus the formation of N4 from dinitrogen is highly endothermic and the reaction does not
proceed as drawn.
 Chem 59-651 Isodesmic Equations: 2 P2 vs. P4
In stark contrast to its lighter analogue, diphosphorus will dimerize to form
P4 (white phosphorus). In doing so, all of the -bonds are replaced with -
bonds. Such behaviour is typical of the all of the heavier elements (n > 2)
in the periodic table.
P
P
2 P P P
P
2 * 490 kJ/mol 6 * 200 kJ/mol
= 980 kJ/mol = 1200 kJ/mol
For example, the relative stabilities of O2 vs. S8:
O-O O=O
207 495 4 O2 O8 Hrxn = +324 kJ/mol

S-S S=S
4 S2 S8 Hrxn = -140 kJ/mol
230 425

These energies are in kJ/mol.

 Chem 59-651 Multiple-bond energy increments
The results of the isodesmic comparisons are often rationalized through
the use of multiple-bond energy increments. These are very rough
approximations (derived empirically) of how much energy is provided by
each element-element single bond versus that of each multiple bond.

For example, the values below suggest that the double bond in O2 should
have a total energy of around 495 kJ/mol because it consists of a bond
(145) and a bond (350). Similarly the energy of the bond in N2 would be
predicted to be 160 + 395 + 395 = 950 kJ/mol.

C-C N-N O-O C-O N-O

335/295 160/395 145/350 335/380 190/370

Si-Si P-P S-S Si-O P-O

195/120 200/145 270/155 452/170 335/150

Ge-Ge As-As Se-Se C-S S-O

165/110 175/120 210/125 280/265 275/250

(in kJ/mol; all values taken from N. C. Norman, 1997) Why do they vary in this way?
 Chem 59-651 Heteronuclear Single Bond Strengths
H-F These energies are in
565 kJ/mol and are very
approximate (all values
Li-F Be-F B-F C-F N-F O-F F-F taken from N. C. Norman,
1997).
573 632 613 485 283 190 155
While the factors
Na-F Mg-F Al-F Si-F P-F S-F Cl-F influencing the strength
477 513 583 565 490 284 142 or weakness of the
homonuclear bonds are
K-F Ca-F Ga-F Ge-F As-F Se-F Br-F still important,
490 550 469 452 406 285 187 electronegativity
differences tend to
Rb-F Sr-F In-F Sn-F Sb-F Te-F I-F strengthen bonds
(Coulombic attraction).
490 553 444 414 402 329 231

(A-B) is the ionic resonance energy

D(A-B),theory = (D(A-A) + D(B-B)) in kJ/mol ((A-B) is in eV)
(A-B) = D(A-B),experimental - D(A-B),theory
A-B A+ B-
XA XB = 0.102 ((A-B)) 0.102 is a conversion from kJ/mol to
eV
 Chem 59-651 Heteronuclear Single Bond Strengths
H-Cl These energies are in
428 kJ/mol and are very
approximate (all values
Li-Cl Be-Cl B-Cl C-Cl N-Cl O-Cl F-Cl taken from Huheey,
Keiter and Keiter, 1993).
464 461 456 328 313 218 250

Na-Cl Mg-Cl Al-Cl Si-Cl P-Cl S-Cl Cl-Cl

407 406 421 381 326 255 240

K-Cl Ca-Cl Ga-Cl Ge-Cl As-Cl Se-Cl Br-Cl

423 429 354 350IV 321 192IV 215
(385)II (243)II
Rb-Cl Sr-Cl In-Cl Sn-Cl Sb-Cl Te-Cl I-Cl
444 469 328III 323IV 315III 310IV 207
(436)I (385)II (249)V (284)II

Note the relative strengthening of bonding to elements in the lower oxidation

states. This (perhaps counter-intuitive) observation is readily understood in
the context of the greater difference in electronegativity between the
element and Cl. Remember that electronegativity is not constant and will be
affected by the molecular environment or oxidation state.
 Chem 59-651
Just so you have a table of Pauling electronegativity values in your notes:

The values of XS, XSe, and XI are all around 2.5. This observation, in
conjunction with the position of I in the periodic table, suggests that S-I
bonds and Se-I bonds will be relatively weak.
 Chem 59-651 Isodesmic Equations: Se-I bonds
The prediction regarding the strength of Se-I bonds Se-Se Se-I
in neutral compounds is correct and such 172 150
compounds were considered unlikely on the basis
of isodesmic equations (energies in kJ/mol): I-I
150

R
Se I
Se Se + I I 2
R
R
172 + 150 kJ/mol 2 * 150 kJ/mol
= 322 kJ/mol = 300 kJ/mol

Thus the reagents would be more stable than the products and the reaction
is not predicted to be favourable in the indicated direction. Note that the
energies of the two R-Se bonds on each side of the reaction are assumed to
cancel those on the other side and can thus be ignored in the calculation.
 Chem 59-651 Isodesmic Equations: Se-I bonds
Despite the prediction, DuMont et. al. (See: J. Se-Se Se-I
Organomet. Chem., 2001, 623, 14, and references therein) 172 150
were able to synthesize such compounds by the
direct reaction of diorganodiselenides with I-I
molecular iodine. 150

R
Se I
Se Se + I I 2
R
R
R = Mes, Keq = 30
R = Tip, Keq = 60
R = Mes*, Keq = 300
R = Trisyl, quantitative

Thus the isodesmic comparison has failed. The reason for this failure is the
assumption that one can neglect all factors other than the changing bond
energies. In this case, the size of the substituents has altered the
thermodynamic preference of the system.
 Chem 59-651 Some Sterically-Demanding Substituents
disyl Mesityl (Mes) E
Tip E
E
Me3Si SiMe3
H

trisyl Supermesityl E
Terphenyl (one kind)
E (Mes*)
E
Me3Si SiMe3
SiMe3
 Chem 59-651 Sterically-Demanding Substituents and
the thermodynamics of Se-I bonds
The bulky substituents alter the thermodynamic preference of the diselenide-iodine
system primarily by destabilizing the diselenide. The destabilization is primarily
enthalpic (H) in that it raises the energy of the diselenide by introducing strain into
the molecule. This strain is manifested in distortions of the metrical parameters
(inter-atomic distances, angles and torsion angles) in both the ligands and the Se-Se
fragments of the molecules. There is also an entropic (S) destabilization because
the presence of the two very large substituents restricts the freedom of motion in the
molecule (vibrations and rotations).

In the Mes*-Se fragment

(Mes*-Se)2 (Trisyl-Se)2 distortions include a non-
Se-Se: 2.348 Se-Se: 2.387 planar benzene ring and an
Se-Se in (Ph-Se)2: 2.287 out-of-plane attachment of the
(all data from the Cambridge Stuctural Database - CSD) aryl group to the Se atom.
 Chem 59-651 Sterically-Demanding Substituents:
Kinetic Shields
The traditional understanding of the stabilizing role of bulky substituents is that these
large groups act as Kinetic Shields that prevent incoming molecules from reacting
with the protected functional group. Such a view implies that the energy of the
product (B) is lower than that of the reagent (A) and that the role of the large
substituent is to raise the activation energy (Ea) for the process. If the activation
barrier is sufficiently large, the process will not occur even though the process is
thermodynamically favourable.

Notice that such process implies that if there

were enough energy to get over the barrier, the
Ea reaction would proceed; this means that species
Energy

A is kinetically stable. While this is a

completely reasonable description for some
types of reactions, it is not valid for others.
A
H Remember: Stability is relative!
B
A situation is only stable in comparison to
Reaction Coordinate another possible situation.
 Chem 59-651 Bulky Substituents:
Thermodynamic and Kinetics
Consider the dimerization of subsituted olefins:
An isodesmic reaction predicts the cyclobutane
should be favoured by around 80 kJ/mol.

R R
R
2
R R R
Energy

R = H, Me R = tBu, Ph R = Mes, Tip, Mes*

(-85, -83) (-7, +19) (+68, +282, +395)
Energies are in kJ/mol from Burford, Inorg. Chem., 1997, 36, 3204.
 Chem 59-651 Bulky Groups and Multiple bonding
Because of the relative weakness of -bonding
between P(III) and N, as evidenced by the multiple P-N
bond energy increments (energies in kJ/mol), 300/185
aminoiminophosphines R2N-P=N-R are generally
susceptible to addition reactions in the presence of
R
secondary amines. R
H H N R
N R
+ N N P
N P
R R R N R
R
R
However, the synthesis of a trisaminophosphine containing only one bulky Mes*
group resulted in the spontaneous elimination of a secondary amine and the
formation of an aminoiminophosphine.
R R
H N R N R H
N P N P + N
R R
Mes* N R Mes*
R
Thus the thermodynamic preference of the system has clearly been reversed
(Burford, Inorg. Chem., 1993, 32, 4988).
 Chem 59-651 Bulky Groups and Drastic Changes
Sterically demanding substituents can also be used to change the thermodynamic
stabilities of systems in even more extreme ways. For example, diphosphines
generally have relatively strong P-P bonds (200 kJ/mol) that remain intact in all
phases.
R R R R
P P P P
R R R R
R = Me For all small R groups

However, the disyl-

substituted
derivative cleaves
spontaneously 2
when it is not in the Melt, Solution or
solid state. Gas Phase
(Hinchley, JACS,
2001, 123, 9045) R = CH(SiMe3)2 Stable Free Radicals

Some multiple bonds can also be R R R R

fragmented into carbenoids in a
similar way. (Lappert, JCS, Dalton., Sn Sn Sn Sn
Solution or Gas
1986, 1551 and 2387) R R Phase R R