Cuaprpn 9: CooRnrNa.

rrox CnnnusrRv I: SrnucruRBs aNn

IsounRs
9.1 Hexagonal: Cr, Cz, Dzn

Hexagonal pyramidal: C, C, Cz',

Trigonal prismatic: C, Cz, Cz

Trigonal antiprismalrc: C, Cz Czn

The structures with C2 symmetry would be optically active.

9.2 ^.
dicyanotetra(methylisocyano)iron(0) or dicyanotetra(methylisocyano)iron(0)
Both methods of naming result in the same name in this case.

b. rubidiurn tetrafluoroargentate(III) or rubidium tetrafluoroargentate( l-)

crs- and trans-carbonylchlorobis(triphenylphosphine)iridium(I) or cls- and trans-
carbonylchlorobis(triphenylpho sphine)iridium(0)

d. pentaammineazidocobalt(III) sulfate or pentaammineazidocobalt(2+) sulfate

e. diamminesilver(I) tetrafluoroborate(lll) or diamminesilver(1+) tetrafluoroborate(l-)

(The BFa- ion is commonly called simply "tetrafluoroborate.")

9.3 a. tris(oxalato)vanadate(Ill) or tris(oxalato)\'anadate(3-) (In the first printing, problem

9.2.d. was duplicated here.)

b. sodium tetrachloroaluminate(III) or sodiltm tetrachloroaluminate( 1-)

c. carbonatobis(ethylenediamine)cobalt(II I ) chloride or
carbonatobis(ethylenediamine)cobalt( 1 +) chloride

d. tris(2,2'-bipyridine)nickel(Il) nitrate or tris(2.2'-bip,vridine)nickel(2+) nitrate (The

IUPAC name of the bidentate ligand, 2.2'-bipl ridy I rnay also be used; this ligand is most
familiarly called "bipy.")

e. hexacarbonylmolybdenum(0) (also cotnmonh'called "molybdenum hexacarbonyl")

The (0) is often omitted. (In the first printing. problem 9.3.c. was duplicated here.)

9.4 a. tetraamminecopper(II) or tetraamminecopperl 2-r-)

b. tetrachloroplatinate(Il) or tetrachloroplatinate(2-)

c. tris(dimethyldithiocarbamato)iron(lII) or tris(dimethyldithiocarbamato)iron(0)

d. hexacyanomanganate(II) or hexacyanomanganate(4-)

nonahydridorhenate(Vll) or nonahydridorhenate(2-) (This ion is commonly called

"enneahydridorhenate. ")
 (n1)runrpelledolulrurpoponpunbetq 'q

T\
>"5-* --'-rv
|
U
(111)o3(ue)srqoxorp,(q-ri-optrue-d -(111)o3(ue)sr g L'6

(-Z)la>lcruorolqcrp(eurpl t,lilq-,7'7)srq ro (11)le4cruorolqcrp(eurprrfdtq-,7'7)stq 'p

.ro (11)iunrueqtm(euturerpeuelfqle)su1
.J
(17)runrueqlru(eunuerpeuel,{qle)s1.r1

(-g)eluqeqocolel€xoslrt ro (111)elelleqocolel€xosIrl 'q

g)urnrueqln.r(oleuleqrecolqtlpl,{qterurp)srq1,{uoqrectp
(

-.!1,7 ro (111)urniueqln-r(olerueq"recolqllpl{qleulp)srq1,(uoqJecIp-sl, 9'6

( g)unrueqr(eunue1,{qletpouItueIp
-,7'7)o:oplcourorqrp :o (111)urnruaqr(eurrue1,{qleIpouItuBIp
-,7' 7)otoyqcouotqtp ro ( g )urn ruatlreulul€lJlouelfqletporolqcoruoJqlp
:o ( 111 )uinruerporrLuuulauel,(qletporolq3oluoJqlp

(g)unrueqr[(eurqdsoqdl,(qleruyp)(eurs.rul,iqlerutp)aua1,(ueqd-7'1]ouorqtp
:o (11)unrueqr[(eurqdsoqdy,{qleurrp)(auts:e1,{q}arurp)euel,{uaqd-7' 1]otuorqtp
ro (g)runrueqr[(eurqdsoqdlfqterurp)(euts.tu1,{q]erurp)aue1f uaqd- ol otuo,iqtp
:o (11)urnrueqr[(eurqdsoqAlfqteulpXeursrelfq]erurp)euelfuaqd-olouto:qtp 'rl

(17)unurleydorolqcouro-rq(1f pu,(dtq
Z)sIq;o (n1)urnurleldo.rolqcotuo.rq(1Xprr,{dr q-,7' 7)stq rc
-,2'
(17)uinurteldorolqcoruorq(eurprr,{d,{q)srq .lo (n1)runupeldorolqcoruorq(aurprrfdrq)stq

(11)runnuorqc(euelorqlueueqd-g 1' 1 )o:olqctpeultutuelp ro

(111)ulnrurorqc(euelorqlueueqd-g 1'1)orolqcrpeurrutu€rp ro (+ I )runrurollc(eurlorqlueueqd
-o)orolqcrpaurtutuerp ro (111)runnuorqc(eur1o:qluuueqd-o)oJolqcIpeuItuIuBIp

( I 3)runutluld(sutruetpeueqle
-7' 1)srqo.royqcrp ro (n1)runurleld(eurruerpaueqle-7' 1)stqoroll{cIp ro
(-;7)runurleld(eururerpeueyfqia)srqo.rolqclp .ro (n1)runurleld(aurtuerpeuel,{q1e)srqorolqclp

(g)urnnuo,rqcopororolqcoruorqenber-r1 :o (111)runrruoJqJopolorolqcotuorqunbet.t1 'p

(11)lleqoco.rolqrotuorqenbetpeututuerp ro (111)lleqosorolqcouorqenbetpeultutuelp

(+ I )lluqocoroyqcrpenberpeurruruerp -ro (11i)lleqocorolqrlpBnbetpeuruturetp 'q

(1 1 )urnurleldo.rolqcr4eulrutueIJ] ro (n1)utnulleldo:olqculeultutuelJl s'6

sJerrrosl pu€ seJnlcnJ]S :1 ,{.tlsluraqJ uoI}suIpJOoJ 6 raldeq3

90 Chapter 9 Coordination Chemistry I: Structure and Isomers

Hzo

oNo---_ ----oH: oNo-_.- | -.--I

n,olf \oro n.oiPf-<-o*o

oNo..-_ | -.OHr

oo,olto

H2o'--"-Dl,{- i-___ | _--.oH:

"'-'l
oNo/'1"\oNo o,.u/io'<."."
Hzo oH.

enantiomers

c. Fe(dtc)3

a\ '\=
S
'\...---/
CHJ

*/ i-\
s---__-l^--..--s
\
/

!l
q./'i\.q
s'
.4',
H

At low temperature. restricted rotation about the C-N bond can lead to additional isomers
as a consequence of the different substituents on the nitrogen. These isomers, which are
of the type in problem 9.1 1. can be observed by NMR.

9.8 triammineaquadichlorocobalt(lll) chloride Isomersareofthecation:

-l + NI].
Hzo

H,o-----_..1
-.---'NH:
c,Z'1o\*",
 .i
*>t /o\
q"' "---_N /
f">t\
\ N----
//"N
-"o
\

\I
|
l
I

o N : -d.' NzH

J-tHJ
//
o
o,\ 0I'6

3{-eJ li
./'o
^,7'\\r/,/ tr'^ ((g)uoll,tuoqrecr:1)srq1,{uoqrec-d -t11

o'or 'o'o
o

zHo1.l, .roNo
'---'ozH
n*o""'--i (n1)urnrpelledolt,tltutpoponpenbetp

t"*\
,/'* (11)runurleldoJolqcotuorqeulultuelp-sr 'v 6'6

" ,/\
.HN .IJ
stu).u sJeluollueue .s!,

ozH o"H
'Ho

ro-.,J..--o
I
\-- | -..u t 4 '"-"1^<"1 (">'i o"H

t)
--o
"o /
-'
\ o" "'-"i- -

_L , O"H _,-\J
.J
:uoluseqlJoer€sJeuosI(111)eleue8ueu(o1e1exo)stqenbetptuntsselod

iHN rHN sHN ^NrH

rux
ni\_-- \ /
\ //
\ \ /.,,n
/-.-
-'J1 I )-

.,1-
+v
,
,.r/-\;?'\-.r,
tHN

uor ((111)urnlulorq J-eultuurelued)srq-oxo-ti 'q

I6 sJeluosl pu€ seJnlJnrlS :1 ,tlsrruaqJ uolleuipJooJ 6 raldeq3

92 Chapter 9 Coordination Chemistry I: Structure and Isomers

t \ I
("j+ \e B._-

"/
\
t---"1
.foc
/ \
*-,)
'-Tj
9.12 a. [P(NH3)3C13]-
NH.
-1 + cll -+
I

cr-.-__. l__-----NH: HrN-.__ | - -.NH:

-'Dr'-
'l'\*", crl'l'\Nu,
",/ I
I
I

CI CI

.fo,

b. fCo(NH:)z(H2o)2clzl-

NH, -+ cl 1+ 1+ NH" -1+

T",
s,o--.-_-!
I

,-,1/L;o\.,'ru.
CI
I
----'NH:
H,o- -
""i1"'<..^n,
CI
|

I
--*",
:-{< ",;1"-",'
NHr NH:

-r* -+
oH" H,O I

riro.-_._..]
I
H,N--- | -.-oH:
--...NHr
.r/t1o\*". u.*'l1o-1..,
I I
CI CI

enantlomers

ICo(NH;):(H2O)2BrCl]-

oH. -1 - cl -+ I NH. 1+
I

n,*_.._. | .-...o, H,o-- I --nn, .,.......1 .....oH.

"'*/J\'' OH,
",">:"-<"", I
Br
",o/lo\".
NH:

OH, -+ H"o -+ I OHr -+ Hzo -+ I

I - --oH" I I

Hro--- |
I

_..Nu, H.N--
" -'-r'^" Hro--_ I _--Nu, H,N.- | --oH,

u,lto-^*, H,N/1"\u, .,,/to-.^n, u."'}1o-",

I I I
I
al CI Br Br
 ---,,

v\-\
rA*---- |
t(
\r'
)l
i

+zL *i L

spue8rl tgp saarr <r;ii1 13 strr-tl

.H\

IJr
IJ
rl
|-
_/'\'u 'H\-. l_ alJ
l
,HN,----ri-=.n A, '.,---:'f

+L
+L

.['tc'(tHN)(ueqd-o)r3]

SUDJI sJeluorlu€uo ,91,

LJ

''>.,!1*)
| "'-N /
(*\,!/''
\ N-"- -"'N

U
\'-' |
\l\l
\_N
--L +zL

*.IzlJz(ue)uJ

,-L I
o:H ,r-. L ozH -
:a ozu

,"o-"--"|"-'-',, 'ro-
--- -"i'-'-" zlo""' ,l
tl
CHO .HO
'
i"""',
zgo

rg r8
I

,r\_,\-/, I .l,\-r\_/,,
tno--"-
i'-"--'o'H 'Ho""" f "-"o'n
I
I I
o'H "HO

IISJgT(OZH)JJ 'p

sJeruosl pue seJqcrul5 :1,{-rlsrrueq3 uorl€ulpJooJ 6 ralduq3

 Chapter 9 Coordination Chemistry I: Structure and Isomers

h. Re(arphos)2Br2 Abbreviating the bidentate ligands As P:

Br
i-\ Ci
Br

(j>+<t) il-+-*: ll>i'--i,

I

1 Y-....o1"..--'t )
\arz \e -.a*z
I

Br
I
Br L) \-i
A A

"i-)
Br-.- |
ci" t1 ci"
Br--- | P--- |

"''i)
---P -.-P -.-Br
i>i"-xl *z|"-n,
A
\-1,
A
IJ \-i
".2\'-o,
A A

Re(dien)B12Cl

C1

Br-.-_
u,i1'\^J
| -.--N-)
t>+--":
[)
(,,-l
Br

., N---_ |
L.,<b. -.--Cl

Br l,
9.13 a. The "softer" phosphorus atom bonds preferentially to the soft metal Pd (see section 6.3.1).

b, c. Abbreviating the bidentate ligands N P :

a1
C1
(-\
/ P-
I

-. -^1,-.,--P \
I

r P'--.-f ----'N I N-- | -.Cl

\1\Iz''f '-.*7 \ru/tlt-.p,/
I
CI
I

C1
t'-Ji-cr
P
 N
ill
ill
J 'sle osl€ ere spue8ry oruoJq eql 'llnser e sy '(e.tr1ce
I

'g\.1_.,/./rs dI eJe seqcte4s o-J crJleuJru,{sr1uu pue culeurur,{s

eql qloq) slfuoqrec eql JoJ eJnlcruls sle e eleclpul
oz=r""
"l [""-'-o spueq O-J o^\l eql epq,l '(e,rr1c€ UI lou sr spuoq N-J
1 oqlJo qclerls culeururfs eq1) seprue.{o eql JoJ oJnlcruls
ltl
suD4 e selecrpur ,(cuenbe4r 8urqc1e4s 51-3 eySurs eq1 SI'6
ill
_L N

V V

o
a-?
:>,[,-]
13" >+<13
J_, \.--j
V V
S
a-i
'r- ||
IC'-
,j-J--N
o- ,ln -t-ll
N'-- 'l' ---'If,
T) t_l
IJ IC

( d- ,L--o \ /N-*,1,_-o
I

\
\ xl""'r*'---s / \ a----',1*'--.g,/
I I

If, IJ
:s o pue d N spue8rl epluaprq eqt Surlerzrerqqy vt'6
\-/ v
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96 Chapter 9 Coordination Chemistry I: Structure and Isomers

9.16 There are 18 isomers overall, twelve with the chelating ligand inamer geometry and six with
the chelating ligand in afac geometry. All are enantiomers. They are all shown below, with
dashed lines separating the enantiomers.

rl/-\ T-\
t\ /-\ T-r
7 P---_ | --.Br Br-----.1.----.P r------ H,N..--_ | ..--..P
1
(A,.iYa.NH. \ 7
n,,u/ \o,z-'j'--oH:
^1,..-.-r'rH,
H.O./'i'-\rAs/
NH:
I
OH:
i'\o"/
OH:
I

T\ \
n,o'----,1..-.-.-o
/-\
P.--_.-1
I\As./'i'\Br
i\
H,N.--__^1"._.---e
,(i^ ..= H,o.-..-1
,'---t
t\
R./'i'\.a./
..---rn3
n'l 1
\o,/ u,r/'i'\'o,/
-..---n 1
-'l
I
NH:
I
OH:
i\e'/
OH:
i'-"n, I

oH,
'f"'
^-(J-----'l ---R
t'---.-^l----'*
/\o,z-'i'\r,rH,
'.o/ i'\o'/ I

9.r7 b. A A d.

9.18 All are chiral if the rins in b does not switch conformations.

9.19 18b 6 l8c top ring: 6, bottom ring: l"

reF
9.20 The doublet is from the two axial fluorines (split by the equatorial fluorine). pl
reF I
The triplet is from the equatorial fluorine (split by the two axial fluorines).

The two doubly bonded oxygens are equatorial, as expected from VSEPR
:>q.-. I
considerations. F

9.21 Examples include both cations and antons:

[Cu(CN)2]-, [Cuz(CN):]-, [Cu3(CN)a]-, [Cua(CN)s]-, [Cus(CN)e]-

"
[Cu2(CN)]*, [Cu3(CN)2]", [Cu+(CN):]*, [Cu5(CN)a]", ICu6(CN)5]

Based primarily on calculations (rather than experimental data), Dance et al. have proposed
linear structures such as the followine.:

[Cu(CN)2] : NC-Cu-CN
ICu2(CN)3]-: NC-Cu-CN-Cu-CN
ICu3(CN)a]-: NC-Cu-CN-Cu-CN-Cu-CN
[Cu2(CN)].: Cu-CN-Cu
ICu3(CN)]-: Cu-CN-Cu-CN-Cu
lCua(CN)31*: Cu-CN-Cu-NC-Cu-CN-Cu
Where 2-coordinate copper appears in these ions, the geometry around the Cu is linear, as
expected from VSEPR.
 0H0)
'\/
0H0)
'\t- 0-0)
'\7

,?40+q?t+";4d'blFr,
)B''l'-( ;':t'
->"h€. ,e*,*(
\ l\. '1\,"
t'[
",,,";
t
*"' Pt' q ",',?o'
J o

/"'

tfiO fq10 tq10

vz'6

('ueSorpfqgo I?tlqro
sI or{l pu€ sle}rqJo urnruoqJ eq} ueel\leq serS"teue ur qc}etu eq} uo puadep osle IIIIv\ suollc€Je}ul
eseqlJo q€ue4s eql) 'uorlceJelur roJ ,{"rleruurfs olq€lrns on€q I€leu eq}Jo sl"llqJo p pue'd
',s eql II€ os 'eg3io slellqJo p pue'd'(,rV Surqcleru 'culetutufs f1ye1o1) ,e roJ suollcunJ oql IIe qcl€lu
suor]€luosoJde:eseql ,{yenr1ce11o3 ',,I *,,7v+,EZ+,tVZolsecnpeJJuoll€luesarde-raql

(zt'zx) 0 I 0 I-
z I I- T- I
;'. '(,{'r)
,{- .r)
: 0 I-
T
0 I- ,T
Iw
0 t I I

t)z 'tte

:sr spuedrl eprrp^q eqlJo

slelrqJo .rl auru eql uo p.sEq J uottetuasaldal V 'rl.O st dno:8 lurod eq1 E7'6

'se:nleradruol
req8rq l€ uenuocJelur qcrq,\\ 'sJeurosr ascrll -lo aruasa;d ar11 iloddns e:nleredruel i!\ol ]e
Bl€p UI trN ('sleporu Suqeur r(q uees eq lseq uBJ sB 'u4-ny-rd 01]uolullnbe st ld-nv-ud)
u4-ny-r4 u4-ny-u6 l6-ny-r4
:elqlssod eJe sJeluosi ee:ql 'ruole plo8 u o1 lueureSuexs JBoUII
e ur peqc€n€ e;e ssurqdsoqd i(1,Qrseur)d o,tlJt 's.le11edord (u4) pepueq lq8u
r\r pue ('1d) pepu€q Uol o1relIuIS se pereplsuoc eq u€c pue (f4eruru,(s ?)
&tlertqc
,roqs uec spue8rl eurqdsoqd eql leql Sutp,u.orc ]uelcgJns esnec sdnor8 1,fitseu f11nq eq1 zz'6

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98 Chapter 9 Coordination Chemistry I: Structure and Isomers

9.25

9.26 a. Cu(acacCN)z: Dzn tpt: C2,

b. Ce