Cuaprpn 9: CooRnrNa.rrox CnnnusrRv I: SrnucruRBs aNnIsounRs

9.1 Hexagonal:

Hexagonal pyramidal:

Trigonal prismatic:

Trigonal antiprismalrc:

9.2 ^.

e.

9.4 a.

b.

c.

d.

Cr, Cz, Dzn

C, C, Cz',

C, Cz, Cz

C, Cz Czn

b.

The structures with C2 symmetry would be optically active.

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

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

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

carbonylchlorobis(triphenylpho sphine)iridium(0)

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

diamminesilver(I) tetrafluoroborate(lll) or diamminesilver(1+) tetrafluoroborate(l-)(The BFa- ion is commonly called simply "tetrafluoroborate.")

tris(oxalato)vanadate(Ill) or tris(oxalato)\'anadate(3-) (In the first printing, problem9.2.d. was duplicated here.)

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

carbonatobis(ethylenediamine)cobalt(II I ) chloride orcarbonatobis(ethylenediamine)cobalt( 1 +) chloride

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.")

hexacarbonylmolybdenum(0) (also cotnmonh'called "molybdenum hexacarbonyl")The (0) is often omitted. (In the first printing. problem 9.3.c. was duplicated here.)

tetraamminecopper(II) or tetraamminecopperl 2-r-)

tetrachloroplatinate(Il) or tetrachloroplatinate(2-)

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

hexacyanomanganate(II) or hexacyanomanganate(4-)

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

d.

e.

a.

b.

c.

d.

9.3

(n1)runrpelledolulrurpoponpunbetq 'q

(111)o3(ue)srqoxorp,(q-ri-optrue-d -(111)o3(ue)sr g

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

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

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

( g)urnrueqln.r(oleuleqrecolqtlpl,{qterurp)srq1,{uoqrectp-.!1,7 ro (111)urniueqln-r(olerueq"recolqllpl{qleulp)srq1,(uoqJecIp-sl,

( g)unrueqr(eunue1,{qletpouItueIp-,7'7)o:oplcourorqrp :o (111)urnruaqr(eurrue1,{qleIpouItuBIp

-,7' 7)otoyqcouotqtp ro ( g )urn ruatlreulul€lJlouelfqletporolqcoruoJqlp:o (

1 1 1 )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

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

(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

(11)lleqoco.rolqrotuorqenbetpeututuerp ro (111)lleqosorolqcouorqenbetpeultutuelp

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

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

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

T\>"5-*| --'-rv

UL'6

'p

.J

'q

9'6

'rl

'p

'q

s'6

90 Chapter 9 Coordination Chemistry I: Structure and Isomers

Hzo

oNo---_ ----oH:

n,olf \orooNo-_.- | -.--In.oiPf-<-o*o

oNo..-_ |

oo,olto-.OHr

H2o'--"-Dl,{- "'-'l

oNo/'1"\oNoi-___ | _--.oH:

o,.u/io'<."."Hzo oH.

enantiomers

c. Fe(dtc)3

a\s---__-l^--..--s \q./'i\.q /!l

S CHJ

'\ '\...---/

*/ = i-\.4',s' H

9.8

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.

triammineaquadichlorocobalt(lll) chloride Isomersareofthecation:

+-lHzo NI].

H,o-----_..1 -.---'NH:

c,Z'1o\*",

\//"N

-"oI

.i*>tq"' l\I

/o\"---_N / f">t\\ N---- |

zHo1.l, .roNo

n*o""'--i '---'ozH

t"*\

,/'*

" ,/\.HN .IJ

stu).u

ozH

I

\-- | -..u 4ro-.,J..--o t\ o" "'-"i-

- -' "o /

o,\ li ./'o3{-eJ^,7'\ ,/ tr'^o'or \r/ 'o'oo

o N : -d.' NzH

J-tHJ//

o

((g)uoll,tuoqrecr:1)srq1,{uoqrec-d -t11

(n1)urnrpelledolt,tltutpoponpenbetp

(11)runurleldoJolqcotuorqeulultuelp-sr 'v

sJeluollueue .s!,

0I'6

6'6

'Ho o"H

'"-"1^<"1

_,-\J(">'i o"H

--ot), O"H_L

:uoluseqlJoer€sJeuosI(111)eleue8ueu(o1e1exo)stqenbetptuntsselod

iHN rHN sHN ^NrH

rux \ / \ /.,,nni\_-- \ // \ /-.--'J1 I )-

,.r/-\;?'\-.r,, tHN

.,1-+vuor ((111)urnlulorq J-eultuurelued)srq-oxo-ti

sJeluosl pu€ seJnlJnrlS :1 ,tlsrruaqJ uolleuipJooJ 6 raldeq3

.J

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I6

92 Chapter 9 Coordination Chemistry I: Structure and Isomers

IB._-

\

\

\e/

t

"/\

-+NH,

Is,o--.-_-! ----'NH:,-,1/L;o\.,'ru.

ICI

-+OH,

I

Hro--- | _..Nu,

u,lto-^*,I

al

("j+ *-,) '-Tj9.12 a. [P(NH3)3C13]-

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

t---"1

oH. -1 -

n,*_.._. | .-...o,

"'*/J\''OH,

-+cll

HrN-.__ | - -.NH:-'Dr'-crl'l'\Nu,

II

CI

T", 1+ NH" -1+

:-{< ",;1"-",'

.foc

-1 +NH.

I

cr-.-__. l__-----NH:

",/ 'l'\*",I

CI

.fo,

cl 1+

H,o- - | --*",

""i1"'<..^n,I

CI

-r*oH"

I

riro.-_._..] --...NHr.r/t1o\*".

I

CI

NHr NH:

-+H,O I

H,N--- | -.-oH:

u.*'l1o-1..,I

CI

enantlomers

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

-+cl I

I

H,o-- I --nn,

",">:"-<"",I

Br

-+OHr

I

Hro--_ I _--Nu,

.,,/to-.^n,I

Br

NH. 1+

.,.......1 .....oH.

",o/lo\".NH:

-+Hzo I

I

H,N.- | --oH,

u."'}1o-",IBr

-+H"o I

H.N-- I --oH"" -'-r'^" -

H,N/1"\u,I

CI

rA*---- | ---,,

v\-\ it( )l+zL \r' *i L

spue8rl tgp saarr <r;ii1 13 strr-tl

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

+L+L

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

sJeluorlu€uo ,91,SUDJI

LJ

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

\l\l\_N

--L

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

,"o-"--"|"-'-',, 'ro- --- -"i'-'-"

'tlCHO .HO

(*\,!/''\ N-"- |

-"'N

U+zL

*.IzlJz(ue)uJ

:a - ,l ozu

zlo""' i"""',zgo

rg

I,r\_,\-/,tno--"-

i'-"--'o'HI

o'H

r8

I.l,\-r\_/,,

'Ho""" f "-"o'nII

"HO

'p

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IISJgT(OZH)JJ

Chapter 9 Coordination Chemistry I: Structure and Isomers

h. Re(arphos)2Br2

Br

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

Br

Abbreviating the bidentate ligands As P:

"i-)Br-.- | ---P"''i)

BrI

(j>+<t)I

Br

ci"i>i"-xl\-1,

A

i-\il-+-*:L)

A

t1Br--- | -.-P

".2\'-o,IJA

t>+--":(,,-l

(-\N-- | -.Cl

t'-Ji-cr

Cill>i'--i,\-i

A

ci"P--- | -.-Br

*z|"-n,\-i

AA

Re(dien)B12Cl

C1

Br-.-_ | -.--N-)u,i1'\^J[)

Br

., N---_ | -.--ClL.,<b.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 :

C1

I

/ P- -. -^1,-.,--P \\1\Iz''f '-.*7

I

CI

a1

I

r P'--.-f ----'N I\ru/tlt-.p,/

I

C1 P

N

illillJ

I

'g\.1_.,/./rs

oz=r"" [""-'-o"l1

ltlill

_L N

V

o

:>,[,-]13" J_,

V

a-?>+<13\.--j

V

a-io-

,ln -t-llN'-- 'l' ---'If,

t_lIJ

( d- ,L--o \\ xl""'r*'---s /I

If,

'sle osl€ ere spue8ry oruoJq eql 'llnser e sy '(e.tr1ce

dI eJe seqcte4s o-J crJleuJru,{sr1uu pue culeurur,{seql qloq) slfuoqrec eql JoJ eJnlcruls sle e eleclpul

spueq O-J o^\l eql epq,l '(e,rr1c€ UI lou sr spuoq N-JoqlJo qclerls culeururfs eq1) seprue.{o eql JoJ oJnlcrulssuD4 e selecrpur ,(cuenbe4r 8urqc1e4s 51-3 eySurs eq1 SI'6

V

S

:s o pue d N\-/ v

ICI

/N-*,1,_-o \\ a----',1*'--.g,/

I

IJ

spue8rl epluaprq eqt Surlerzrerqqy

'r- ,j-JIC'- | --N| --N

T)

sJeruosl pu€ seJnlcruls :I,{.rlsrrueqc uor}€urpJooS 6 ralduq3

vt'6

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 withthe chelating ligand in afac geometry. All are enantiomers. They are all shown below, withdashed lines separating the enantiomers.

/-\rl7 P---_ | --.Br(A,.iYa.NH.

I

OH:

/-\I P.--_.-1 ..---rn3\As./'i'\Br

I

OH:

oH,

---R/ t'---.-^l----'*\o,z-'i'\r,rH,

I

T-\t\Br-----.1.----.P \n,,u/

i'\o"/OH:

i\H,N.--__^1"._.---e 1n'l i\e'/

OH:

/-\7 r------ ^1,..-.-r'rH,\o,z-'j'--oH:

T-rH,N..--_ | ..--..P 1H.O./'i'-\rAs/

I

,'---tt\H,o.-..-1 -..---n 1u,r/'i'\'o,/

I

,(i^ ..=\o,/ i'-"n,

'f"'

^-(J-----'l'.o/ i'\o'/

9.r7 A

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"

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

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

The two doubly bonded oxygens are equatorial, as expected from VSEPRconsiderations.

9.21 Examples include both cations and antons:

NC-Cu-CNNC-Cu-CN-Cu-CNNC-Cu-CN-Cu-CN-Cu-CNCu-CN-CuCu-CN-Cu-CN-CuCu-CN-Cu-NC-Cu-CN-Cu

d.Ab.

plI

:>q.-.IF

[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] :

ICu2(CN)3]-:

ICu3(CN)a]-:

[Cu2(CN)].:

ICu3(CN)]-:

lCua(CN)31*:

Where 2-coordinate copper appears in these ions, the geometry around the Cu is linear, as

expected from VSEPR.

NH:

T\n,o'----,1..-.-.-o \R./'i'\.a./-'l

I

NH:

0H0) 0H0) 0-0)'\/ '\t- '\7

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

l\. '1\," /"'

tfiO fq10 tq10vz'6

('ueSorpfqgo I?tlqrosI 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)z

,{- .r) '(,{'r): ;'.

0

I0

0

II-I-Tt

I-II-I

,TIw

0T-

0

I

t)z

:sr spuedrl eprrp^q eqlJoslelrqJo .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 ]eBl€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 lq8ur\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

'tte

sJeruosl pu€ seJnlcru1s :1,ft1srueqJ uoli€ulprooJ 6 ralduq3

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98

9.25

Chapter 9 Coordination Chemistry I: Structure and Isomers

a.

b.

Cu(acacCN)z: Dzn

Ce

tpt: C2,9.26