INORGANIC CHEMISTRY

Coordination Compounds
A Lewis base (e
-
donor) donates a pair of electrons to a Lewis acid (e
-
acceptor) forming a
co-ordinate covalent bond.
Ammonia is the Lewis base (electron donor). H
+
and BF3 are Lewis acids (electron acceptors).
imilarl!" transition metals and their cations are Lewis acids. #he! have vacant orbitals that can
accept electron pairs from donor atoms (Lewis bases) forming coordination compounds or
complexes. ome e$amples are shown in the following table.
Lewis Acid Lewis Base Comple !issociation Constants
%r
+3
+ &H'( )%r((H')&*
+3
-------------
%o
+3
+ &+H3 )%o(+H3)&*
+3
'.' ,-
-3.

+i
+'
+ .%+
-
)+i(%+).*
-'
,.- ,-
-3,

Fe + /%( )Fe(%()/* -------------
Ag
+
+ '+H3 )Ag(+H3)'*
+
&.3 ,-
-0

Lewis bases (anions or molec1les) bonded to the central Lewis acid are called li"ands (Latin 2
tie or bind). %harged coordination comple$es also have counter ions associated with them to
satisf! electrone1tralit!. For e$ample" in )Ag(+H3)'*
+
+(3
-
" a nitrate anion is the co1nter ion.
%o1nter ions are ionicall! bonded. 3hen dissolved in water" the +(3
-
ion separates from the
comple$" b1t the two +H3 ligands remain firml! bo1nd to the Ag
+
ion b! covalent bonds.
#he n1mber of atoms bonded to the central ion4atom of a coordination comple$ is referred to as
its coordination num#er. #he coordination n1mber of )Ag(+H3)'*
+
+(3
-
is two. #he coordination
n1mber of )Fe(%()/* is five. %oordination comple$es occ1r with coordination n1mbers of '
thro1gh ,'" however" coordination n1mbers of '" . and & are most common.
%omple$es s1ch as )Fe(%()/* are 1s1all! insol1ble in water since the! are covalent compo1nds
in which an! dipoles cancel. %omple$es s1ch as )Ag(+H3)'*
+
+(3
-
are generall! ver! sol1ble in
water since the! are made 1p of cations" e.g." )Ag(+H3)'*
+
and anions" e.g." +(3
-
.
Importance o$ Coordination Complees%
5an! biologicall! important s1bstances are 6d6-transition metal coordination compo1nds that are
made 1p of large organic molec1les bo1nd to the metal via coordinate covalent bonds" e.g."
hemoglobin (blood protein) is a coordination comple$ involving Fe.
vitamin B-,' is a cobalt comple$ (c!anocobalamin)
phthaloc!aine bl1e is a %1 comple$ d!e 1sed for bl1e 7eans and in8
Coordination Complees
,
ammonia
N
H
H
H
% & B
'
'
'
N
H
H
H
B
'
'
'
Boron (as a )acant *p+ or#ital,
Nitro"en (as a $ull sp - or#ital,
A co.ordinate co)alent #ond is $ormed
w(en nitro"en donates its lone e
.
pair
to #oron/s empt0 *p+ or#ital,
N
sp- or#itals
sp* or#itals
*p+
B
H
&
H0dro"en ion (as a )acant 1s or#ital,
Nitro"en (as a $ull sp - or#ital,
A co.ordinate co)alent #ond is $ormed
w(en nitro"en donates its lone e
.
pair
to (0dro"en/s empt0 1s or#ital,
ammonia
ammonium ion
N
H
H
H
% & H
&
N
H
H
H
H
&
N
sp- or#itals
1s
2
H H H
1s11s11s1
INORGANIC CHEMISTRY
comple$ing agents are 1sed for water softening (%a" 5g" Fe removal with 9:#A)
an antidote for some metal poisoning (BAL) forms comple$es with As" Hg" and %r.
Fe-carbon!ls are anti-8noc8 gasoline additives
Structure o$ Coordination Compounds%
tr1ct1res are determined b! the coordination number and ;9<=. Lone pairs of e
-
6s in
d-orbitals have minimal infl1ence on geometr! beca1se the! are not in the o1ter shell.
>n the following table" ?%o @A refers to coordination n1mber of the central atom or ion.
Geometries o$ 3arious Coordination Num#ers
Co4 Geometr0 H0#ridi+ation
5nonmetals6
H0#ridi+ation
5transition
metals6
Eamples
5transition metals6
' sp (BeH') sp
)Ag(+H3)'*
+
)%1(%+)'*
-
. sp
3
(%H.) sp
3
)Bn(%+).*
-'
)%d(+H3).*
+'
)Fe%l.*
-
)%o(Br).*
-'
. sp
3
d
'
(CeF.) dsp
'
)<d(%().*
+'
)<t(+H3)'%l'*
)+i(%+).*
-'
/ sp
3
d (<%l/) d
3
sp or dsp
3
or sp
3
d
)%1%l/*
-3
)Fe(%()/*
)5n(%().+(*
)+i(%+)/*
-3
& sp
3
d
'
(F&) d
'
sp
3
or sp
3
d
'
)<t%l&*
-'
)%o(+H3)&*
+3
)Fe((H')&*
+'
)Fe(%+)&*
-.
)5oF&*
-
)%oF&*
-3
)+i(H'()&*
+'
)5n(%+)&*
-.
%o @D )EFD*
-3
" )BrFD*
-3
" %o @0 )5o(%+)0*
-.
" )#aF0*
-3
and %o @F )E%l3 h!drate* are 8nown b1t rare.
Coordination Complees
'
linear
1*27
827
e
e
e
a
a
trian"ular #ip0ramidal
e 9 e:uitorial position
a 9 aial position
827
827
octa(edral
128,;7
tetra(edral
827
s:uare planar
827
Increasin" a#ilit0 to donate an electron pair to a metal ion
INORGANIC CHEMISTRY
T0pes o$ Li"ands%
Ligands of comple$ ions are molec1les and4or ions with one or more donor atoms that each
donates a lone pair of electrons to the metal ion to form a covalent bond. #h1s" ligands are Lewis
bases" the metal ion is a Lewis acid" and the comple$ is a Lewis adduct. Beca1se the! have at
least one lone pair of electrons" donor atoms often come from Gro1ps /A" &A" or DA.
Ligands are classified in terms of the n1mber of donor atoms" or 6teeth6 that each 1ses to bond to
the central metal ion.
Unidentate ligands (Latin" 6one-toothed)" s1ch as %l
-
and +H3 1se a single donor atom.
Bidentate ligands have two donor atoms" each of which bond to the central metal ion.
Polydentate ligands have more than two donor atoms.
ome common ligands in coordination compo1nds are shown below. +ote the lone pair of
electrons in each donor atom. Bidentate and pol!dentate ligands give rise to comple$es with ring
str1ct1res. For e$ample" eth!lenediamine (abbreviated en) has a chain of fo1r atoms
(H+-%-%-+H)" so it forms a /-membered ring. 1ch ligands seem to grab the metal ion li8e a
crab6s claw" so comple$ ions that contain them are sometimes called chelates (Gree8 chela 2
crab6s claw).
Relati)e Stren"t(s o$ Li"ands%
Lewis bases differ in their abilit! to donate electrons to the metal ion. #he relative strengths of
ligands in coordination comple$es has been e$perimentall! determined I
>
-
J Br
-
J %l
-
J F
-
J (H
-
J %'(.
-'
J H'( J %+
-
J +H3 J en J +('
-
J %+
-
J %(
Coordination Complees
3
STRONG
LIGAN!S
<EA=
LIGAN!S
>nidentate
Bidentate
?ol0dentate
H
*
O
,,
,,
NH
-
% Cl
% %
,,
,,
.
'
,,
,,
% %
.
%C N%
.
c0anide ion
%S C N%
,,
.
t(ioc0anate ion
,,
,,
%O N O%
.
nitrite ion
%O H
,,
,,
.
(0droide ion
H
*
C CH
*
H
*
N
NH
*
,,
,,
et(0lenediamine 5en6
C C
O
O
O O
% % % %
,, ,, .
.
%
%
% %
oalate ion
diet(0lenetriamine
H
*
C CH
*
H
*
N
NH
,,
,,
CH
*
CH
*
NH
*
,,
.
.
.
et(0lenediaminetetracetate 5E!TA6 ion
CH
*
CH
*
N N
CH
*
C
O
O
CH
* C
O
O
H
*
C C
O
H
*
C
C
O
O
O
% %
% %
% %
% %
% %
%
%
%
%
,,
,,
,,
,,
,,
,,
,,
,,
.
,,
INORGANIC CHEMISTRY
Nomenclature o$ Coordination Compounds%
Lewis bases ma! be anions" molec1les" or (rarel!) cations and are called 6 ligands6. #he donor atom is the
atom of the ligand" which act1all! donates the electrons (1nderlined in the table). )K 2 bidentate ligands*
$ormula name li"and name $ormula name li"and name
H+H3 ammonia ammine %l
-
chloride chloro
H'( water aL1a F
-
fl1oride fl1oro
H%(H
carbon mono$ide carbon!l H%+H
-
c!anide c!ano
H<H3 phosphine phosphine (H
-
h!dro$ide h!dro$o
H+2( nitric o$ide nitros!l H+('
-
nitrite nitro (+('
-
)
+(3
-
nitrate nitrato H+('
-
nitrite nitrito ((+(
-
)
+H'
-
amide amido K(.
-'
s1lfate s1lfato
K%'(.
-'
o$alate o$alato %+
-
thioc!anate thioc!anato
K%(3
-'
carbonate carbonato K'(3
-'
thios1lfate thios1lfato
K(
-'
o$ide o$o %/H/+H p!ridine p!ridine
Coordination num#er of a metal is the n1mber of donor atoms to which the metal is bonded. >f the
ligands are 1nidentate" then the coordination n1mber is also the n1mber of ligands. For e$ample" in
)%o(en)3*
+3
where each eth!lenediamine ligand is bidentate" the coordination n1mber is &" i.e." %o
+3
is
bonded to & donor atoms (' donor atoms from each of 3 eth!lenediamine ligands).
Coordination sp(ere is the metal and its ligands b1t not the 1ncoordinated co1nterions" e.g." in
)%o(+H3)&*%l3" the coordination sphere 2 )%o(+H3)&*
+3
.
Nomenclature Rules%
,. >f the comple$ is ionic" name the cation first and the anion second.
'. 3ithin a coordination sphere" name the ligands before the metal
3. +ame ligands alphabeticall!" e.g." ammine before chloro. <refi$es denoting the n1mber of ligands
(e.g." di in dichloro" tri in triammine" etc.) are not alphabetiMed" however" prefi$es which are part of the
ligand name are alphabetiMed" e.g." in dimeth!lamine )+H(%H3)'* " di is part of the ligand name and so
is alphabetiMed.
.. <refi$es bis" tris" tetrakis, pentakis," etc. are 1sed for ligands that are bidentate" pol!dentate or alread!
have a n1mber prefi$ as part of its name" e.g." bis(dieth!lamine) has ' gro1ps of dieth!lamine and
tris(o$alato) beca1se o$alato is bidentate. <refi$es are not alphabetiMed. :ivalent anions are bidentate.
anionic ligands end in the s1ffi$ 'o'" e.g." K'(3
-'
2 thios1lfato" K
-'
2 s1lfido" K%(3
-'
2 carbonato
names of ne1tral ligands li8e phosphine (<H3) are 1s1all! 1nchanged e$cept for +H3 (ammine)" H'(
(aL1a)" %( (carbon!l)" and +( (nitros!l)
/. For metals with m1ltiple o$idation states" indicate the o$idation state in =oman n1merals in
parentheses following the name of the comple$ ion or molec1le.
&. 3hen the comple$ is ne1tral or cationic" the name of the central metal atom is the same as the
element" e.g." chromi1m" nic8el" iron
D. For anionic comple$es" the s1ffi$ -ate is added to the stem of the metal name" e.g." Mincate.
Latin names of metals are 1sed when the 9nglish name is cl1ms!" i.e."
ferrate not ironate
pl1mbate not leadate
stannate not tinate
a1rate not goldate
argentate not silverate
c1prate not copperate
chromate
platinate
nic8elate
Mincate
manganate
al1minate
Coordination Complees
.
INORGANIC CHEMISTRY
<RITING NAMES O' COOR!INATION COM?LE@ES 'ROM 'ORM>LAS
($idation n1mber is given onl! for metals with more than one possible o$idation state. For Ag+" the o$@ is not stated.
Ligands are listed alphabeticall!. #he metal ion is listed after all ligands.
+ote that for anionic comple$es (onl!)" the s1ffi$ NateO is added to the metal and the Latin name of the metal is 1sed in some cases
(where pron1nciation of the 9nglish name is aw8ward).
<refi$es di" tri" tetra" penta" he$a" hepta" etc. are 1sed when more than one of a monodentate ligand is present.
<refi$es bis" tris" tetra8is" penta8is" he$a8is" hepta8is" etc. are 1sed for bidentate or pol!dentate ligands" or when the monodentate
ligand alread! has a prefi$ in its name" e.g." bis(dimeth!lamine)
For +amesH note the space between cationic coordination sphere and the anion and between cation and anionic coordination
sphere.
For Form1lasH note that there are no spaces in form1las.
CATIONIC COM?LE@ES
e.g." )%1(+H
3
)
'
*+(
3

cationic coordination sphere anion

ligandsmetal(o$@) anion
diamminecopper(>) nitrate
NE>TRAL COM?LE@ES
e.g." )%1((+()
'
*
ne1tral coordination sphere
ligandsmetal(o$@)
dinitritocopper(>>)
ANIONIC COM?LE@ES
e.g." P
'
)%1(%+)
.
*
cation anionic coordination sphere
cation ligandsmetalate(o$@)
potassi1m tetrac!anoc1prate(>>)
INORGANIC CHEMISTRY
Cationic Complees%
)%o(+H3)&*%l3 he$aamminecobalt(>>>) chloride
)<t(+H3).%l'*
+'
tetraamminedichloroplatin1m(>;) ion
)Ag(+H3)'*
+
diamminesilver ion
)%r(H'().%l'*%l tetraaL1adichlorochromi1m(>>>) chloride
)%o(H'+%H'%H'+H')3*'((.)3 tris(eth!lenediamine)cobalt(>>>) s1lfate
)Fe(H'()/(%+)*(. pentaaL1athioc!anatoiron(>>>) s1lfate
)%1(+H3)'(en)*Br' diammineeth!lenediaminecopper(>>) bromide
Neutral Complees%
)<t(+H3)'%l.* diamminetetrachloroplatin1m(>;)
)%o(+H3)3(+(')3* triamminetrinitrocobalt(>>>)
)+i(H'+%H'%H'+H')'%l'* dichlorobis(eth!lenediamine)nic8el(>>)
)+i(%().* tetracarbon!lnic8el(-) or nic8el tetracarbon!l
)%o'(%()0* octacarbon!ldicobalt(-) or dicobalt octacarbon!l
Anionic Complees%
P3)%o((+()&* potassi1m he$anitritocobaltate(>>>)
)<t%l&*
-'
he$achloroplatinate(>;) anion
+a')n%l&* sodi1m he$achlorostannate(>;)
P')%1(%+).* potassi1m tetrac!anoc1prate(>>)
+a')%r(F.* sodi1m tetrafl1oroo$ochromate(>;)
+a)Al((H).* sodi1m tetrah!dro$oal1minate
+a')n((H)&* sodi1m he$ah!dro$ostannate(>;)
P.)+i(%+)'(o$)'* potassi1m dic!anobis(o$alato)nic8elate(>>)
In $ormulas%
>n the coordination sphere" the metal s!mbol is written first" followed b! s!mbols of its ligands
%omple$ ligands are p1t in parenthesis" even if there is onl! one ligand is present" e.g." (%+)
and ((H). 5onatomic ligands li8e %l" Br" etc. are not parenthesiMed.
>E<A% r1les state
inorganic ligands are listed before organic ligands
anionic ligands are listed before ne1tral ligands
#his last r1le can lead to contradictor! sit1ations. >ndeed literat1re is rife with e$amples where
both these r1les are ignored. >n form1las" it is generall! accepted that it is more important to list
the ligands correctl! than to place them in order. #his lenienc! is not applied to order of listing
ligands in naming the compo1nds. Follow the r1les caref1ll! for naming compo1nds.
+ame the following coordination compo1ndsH
)%o(en)'Br'*%l
)%o(<H3)3*(+(3)3
);(+H')'(+()'*%l3
P')5nQ+H(%H3)'R.(%'(.)'*
)%r(en)/(%+)*F'
+a')5o(%l.*
INORGANIC CHEMISTRY
Coordination Num#er and Geometr0 o$ Coordination Compounds%
+o single theor! is able to s1ccessf1ll! predict the coordination n1mber or geometr! of all
coordination comple$es. +o strict r1les can be stated" however" the following generaliMations are
helpf1l.
#he most common coordination n1mber of metal comple$es is &" e.g." )<t(%l)&*
+'
. 5ost of
these are octahedral. %r
+3
(d
3
)" %o
+3
(d
&
)" Fe
+'
(d
&
)" and Fe
+3
(d
/
) favor octahedral comple$es
regardless of the ligands present. For all di- and tri-positive ,
st
series transition metals" aL1a
ions are octahedral" i.e." )5(H'(&*
+' (or +3)
.
.-coordinate comple$es are the ne$t most common. #he! e$ist in two geometries" tetrahedral
(sp
3
h!bridiMed) and sL1are planar (dsp
'
h!bridiMed). #etrahedral geometries (bond angles 2
,-F./) are stericall! favored over sL1are planar (bond angles 2 F-).
.-coordinate comple$es of non transition metals are almost alwa!s tetrahedral" e.g." )Al%l.*
-
and nBr..
.-coordinate comple$es of the transition metals ma! e$ist in either form. #etrahedral
comple$es are especiall! favored when ligands are wea8 and relativel! large (e.g." Br
-
) and
metal ions are relativel! small" i.e." ,
st
transition metal series comple$es" e.g." ;%l." )Fe%l.*
-
"
)+iBr.*
-
" )5n%l.*
-'
" )%d%l.*
-'
.
+i
+'
(3d
0
) displa!s sL1are planar geometr! with small strong ligands li8e %+
-
" tetrahedral
comple$es with large wea8 ligands li8e F
-
" %l
-
" Br
-
" >
-
and forms octahedral comple$es with +H3
and H'(.
L1are planar comple$es are more common for larger d
0
transition metals" i.e." <d
+'
(.d
0
)"
<t
+'
(/d
0
)" and A1
+3
(/d
0
). teric constraints are rela$ed with these larger metal ions. Less
commonl!" sL1are planar comple$es are also seen with %o
+'
(d
D
)" %o
+3
(d
&
) and %r
+'
(d
.
).
'-coordinate transition metal comple$es (sp h!bridiMed) are restricted to +, ions of Gro1p >B"
i.e." %1
+
(3d
,-
)" Ag
+
(.d
,-
) and A1
+
(/d
,-
) and +' ions of Gro1p 'B" i.e." Bn
+'
" %d
+'
and Hg
+'
.
(dd coordination n1mbers (,"3"/) are ver! rare.
+ote that a given transition metal ion can form comple$es of differing coordination n1mbers.
%o
+'
(3d
D
) forms both octahedral and tetrahedral comple$es
+i
+'
(3d
0
) forms octahedral" tetrahedral" and sL1are planar comple$es (as previo1sl! stated).
3alence Bond T(eor0 o$ Transition Metal Coordination Compounds%
;B theor! treats metal to ligand (donor gro1p) bonds as coordinate covalent bonds" formed when
a filled orbital of a donor atom overlaps with an empt! h!brid orbital on the central metal atom.
#he molec1lar geometr! is predicted 1sing ;9<=.
#he theor! proposes that the n1mber of metal-ion h!brid orbitals occ1pied b! donor atom lone
pairs determine the geometr! of the comple$es. Lone pairs of electrons are ignored. ince lone
pairs are in the inner shell" the! are believed to have little effect on molec1lar geometr!.
*.Coordinate Compounds%
Linear sp (0#ridi+ed transition metal complees%
a. %onsider )Ag(+H3)'*
+
Ag 2 /s
,
.d
,-
Ag
+
2 /s
0
.d
,-

A"
&
Ad ;s ;p
(0#ridi+ed
sp
BA"5NH
-
6
*
C
&
sp ;p
%NH
-
%NH
-
INORGANIC CHEMISTRY
b. %onsider )%1(%+)'*
-
%1 2 .s
,
3d
,-
%1
+,
2 .s
0
3d
,-

?ro#lem% <redict the h!bridiMation state and molec1lar geometr! of )A1%l'*
-
+ote that when transition metals ioniMe" electrons from the (n+,)s orbitals are usually removed
before those of the nd orbital (even tho1gh the (n+,)s orbital is filled before the nd orbital).
#his behavior can be abbreviated as F>F( (First >n" First (1t" i.e." (n+,) orbitals are first to be
filled when b1ilding 1p the electron config1ration of the ne1tral atom" and first to be emptied
d1ring ioniMation).
#he preferential removal of (n+,)s electrons is not s1rprising" since the (n+,)s electrons are
farther from the n1cle1s (held less strongl!) than nd electrons.
'our Coordinate Compounds% 5Tetra(edral Complees6
a. %onsider )Bn%l.*
-'
Bn 2 .s
'
3d
,-
Bn
+'
2 .s
0
3d
,-

b. %onsider )%d(+H3).*
+'
%d 2 /s
'
.d
,-
%d
+'
2 /s
0
.d
,-

+ote that all .-coordinate comple$es of a s
0
d
,-
ion are sp
3
h!bridiMed and tetrahedral" e.g."

.-coordinate comple$es of Gro1p 'B 5

+'
ionsH Bn
+'
" %d
+'
" Hg
+'

.-coordinate comple$es of Gro1p ,B 5

+,
ionsH %1
+,
" Ag
+,
" A1
+,

Cu
&
-d As Ap
(0#ridi+ed
sp
BCu5CN6
*
C
.
sp Ap
C N
% %
.
=
&
CN
.
CN
.
Dn
&*
-d As Ap
(0#ridi+ed
BDnCl
A
C
.*
sp-
sp-
Cl
.
Cl
.
Cl
.
Cl
.
tetra(edral
Cd
&*
Ad ;s ;p
(0#ridi+ed
BCd5NH
-
6
A
C
&*
sp-
sp-
tetra(edral
NH
-
,,
NH
-
,,
NH
-
,,
NH
-
,,
INORGANIC CHEMISTRY
>n fo1r coordinate comple$es of s
-
d
0
ions (+i
+'
" <d
+'
" <t
+'
)" two molec1lar geometries are
enco1ntered" tetrahedral (sp
3
) and sL1are planar (dsp
'
).
%onsider )+i%l.*
-'
+i 2 .s
'
3d
0
+i
+'
2 .s
-
3d
0

As in previo1s e$amples of tetrahedral" sp
3
h!bridiMed comple$es" the ligand donates electrons to
the vacant sp
3
h!brid orbitals. #his is tr1e when large" wea8 ligands are present. However" with
small" strong ligands" s1ch as %+
-
" two 1npaired electrons in half-filled 3d orbitals are forced to
pair 1p with each other" creating an empt! 3d orbital. #his gives rise to dsp
'
h!bridiMation and the
sL1are planar geometr! seen in the following e$amples.
'our Coordinate Compounds% 5S:uare ?lanar Complees6%
3hen ver! strong ligands are present" fo1r-coordinated d
0
metal ions usually form sL1are planar
comple$es (rather than tetrahedral).
%onsider )+i(%+).*
-'
+i 2 .s
'
3d
0
+i
+'
2 .s
0
3d
0

>n dsp
'
h!bridiMation" one d-orbital is empt! and receives an electron pair from the ligand. :onor
atoms are sit1ated on the $ and ! -a$es of the sL1are planar str1ct1re.
+ote that in the term 6dsp
'
6" 6d6 precedes 6sp
'
6 indicating that the d-orbital 1sed in h!bridiMation
comes from a lower (inner) shell than the 6s6 and 6p6 orbitals. #his is called inner s(ell
(0#ridi+ation. >n the previo1s 1nit on bonding" we saw terms s1ch as 6sp
3
d6. >n this case" where
6d6 follows 6sp
3
6" the d-orbital is from the highest energ! level" e.g." recall that <%l/ has sp
3
d
h!bridiMation (triang1lar bip!ramidal geometr!). #his is called outer s(ell (0#ridi+ation,
Si Coordinate Complees 5Octa(edral6%
i$ ligand donor atoms in an octahedral comple$ are located at the corners of an octahedron.
;alence bond post1lates that the orbitals best shaped and best oriented to receive electron pairs
from these directions are the d$'-!' and dM' orbitals (directed on the $" !" and M-a$es).
%onsider )Fe(%+)&*
-3
Fe 2 .s
'
3d
&
Fe
+3
2 .s
-
3d
/
As Ap
(0#ridi+ed
BNiCl
A
C
.*
Ni
&*
-d
sp-
tetra(edral
-d
sp-
(0#ridi+ed
B'e5CN6
E
C
.-
d*sp-
-d
octa(edral
'e
&-
-d As Ap
As Ap
'e
&-
-d
d*sp-
CN
.
CN
.
CN
.
CN
.
CN
.
CN
.
As Ap
-d
As Ap
(0#ridi+ed
BNi5CN6
A
C
.*
dsp*
s:uare
planar
Ni
&*
-d -d
dsp* Ap
CN
.
CN
.
CN
.
CN
.
INORGANIC CHEMISTRY
%+
-
is a strong field donor" forcing inner 3d electrons into a lower spin state and h!bridiMing
inner 3d orbitals" i.e." d
'
sp
3
(inner shell hybridization). H'(" a wea8er field donor" is not able to
bring abo1t inner shell h!bridiMation and the res1lting h!bridiMation is th1s sp
3
d
'
. Both d
'
sp
3
and
sp
3
d
'
comple$es are octahedral.
%onsider )Fe(H'()&*
+3
Fe 2 .s
'
3d
&
Fe
+3
2 .s
-
3d
/

5etal ions in which two d-orbitals are vacant will form inner shell h!bridiMed d
'
sp
3
octahedral
comple$es.
5etal ions in which two d-orbitals are not vacant will form either o1ter shell sp
3
d
'
h!bridiMed
octahedral comple$es (with wea8 ligands) or inner shell d
'
sp
3
h!bridiMed octahedral comple$es
with strong ligands (>f half-filled d-orbitals are present a low spin state can be forced).
t1d! the following e$amples and note where inner and o1ter shell h!bridiMation occ1r and wh!.
As Ap
'e
&-
-d
(0#ridi+ed
octa(edral
sp
-
d
*
Ad
B'e5H
*
O6
E
C
&-
sp
-
d
*
H
*
O H
*
O H
*
O H
*
OH
*
O H
*
O
-d Ad
d
;
Mn
&*
BMn5CN6
E
C
.A
Ad
As Ap
-d

d
*
sp
-
d
F
Ni
&*
BNi5H
*
O6
E
C
&*
Ad
As Ap
-d
sp
-
d
*

d
-
Ad
As Ap
-d

d
*
sp
-
Cr
&-
BCr5NH
-
6
E
C
&-
d
E
Co
&-
BCo5NH
-
6
E
C
&-
BCo'
E
C
.-
stron" li"and
weaG li"and
Ad
As Ap
-d
sp
-
d
*

Ad
As Ap
-d

d
*
sp
-

9 an electron pair donated $rom a li"and

INORGANIC CHEMISTRY
Sample ?ro#lems%
1, :raw the Lewis str1ct1re of the prod1ct of the following
<H3 + AlBr3
3rite the form1la of the Lewis acidH IIIIIIIIIIIIIII.
3rite the form1la of the Lewis baseH IIIIIIIIIIIIIII
*, %onsider )Hg(%+)'*
a6 name it IIIIIIIIIIIIIIIIIIIIIIIIIIII
#6 state its molec1lar geometr! IIIIIIIIIIIIIIIIIII
c6 name its h!bridiMation state IIIIIIIIIIIIIIIIIII..
d6 1se ;alence Bond theor! to show how it bonds

-, %onsider )Bn>3*
-
" a 3-coordinate comple$
a6 name it IIIIIIIIIIIIIIIIIIIIIIIIIIII
#6 predict its molec1lar geometr! IIIIIIIIIIIIIIIIIII
c6 predict its h!bridiMation state IIIIIIIIIIIIIIIIIII..
d6 1se ;alence Bond theor! to show how it bonds
INORGANIC CHEMISTRY
A, %onsider )+i(%+)/*
-3
" a /-coordinate comple$
a6 name it IIIIIIIIIIIIIIIIIIIIIIIIIIII
#6 predict its molec1lar geometr! IIIIIIIIIIIIIIIIIII
c6 1se ;alence Bond theor! to show how it bonds ass1ming inner shell h!bridiMation
;, +ame the following comple$esH
a6 P)b(%'(.)'(+H')'*
#6 )5n((H)'Q+H(%H3)'R.Br*((.)'
c6 P)BF.*
d6 )3(%()'(+(')3F*(+(3)'
E, 3rite form1las for the following comple$esH
a6 potassi1m he$afl1oroantimonate(;)
#6 sodi1m octac!anomol!bdate(>;)
c6 tetraamminediaL1aMirconi1m(>;) bromide
d6 nitratodiphosphinethioc!anatopalladi1m(>;) nitrate