Chapter20:ReactionsofComplexes(Mechanisms)

Twomaintypeswillbecovered:
Ligand substitution
Metalcenteredchemistry
Redox
Athirdtypeinvolvesreactionsattheligands (metalcoordinationmay
enhanceorchangethereactivityofan(in)organicmolecule(e.g.benzene)
Ligand substution reactionsareextremelyabundantandareimportant
propertiesinfluencingtheapplicationsofmetalcomplexesforcatalysis
(chemicalandbiochemical!)

L' + [[ML6]n+

L + [[ML5L']]m+

Whichismorestable?Askyourself:Withrespecttowhat?
Kinetics?
Labile(fastreaction)
Inert(slowreaction)
Thermodynamics?
Stable
G!
Unstable
1

ReviewofRateLawsandKinetics(Chem 1051)

YoushouldreviewPetrucci 9EChapter14(Kinetics)&Ch24(Coord.Chem.)
Thegeneralizedratelawforanyreactionis(where[A]=concn ofA):

Dis nguishingthecaseswhenn=1andn1andsolvingforA(t):
1st orderratesgivelinearln A vs.t plots
Fornth orderratestheplotofA(1n)vs.t is
linear E g when n = 2:
linear.E.g.whenn=2:

If[A]canbeaccuratelymeasuredoverawiderangeofconversions,thisisa
goodwayofdeterminingthereactionorderofA
d
fd t
i i th
ti
d
fA
Oftenthisisnotpossible.Anotherwayofdeterminingthereactionordersof
individualcomponentsofareactionistheMethodofInitialRates:

Thegeneralratelaw

Theratelawforareaction(formationofcompoundA)withseveral
componentsis:

IfweholdconcentrationsofB,C,D,andallotherparameters(T,P,etc.)
constant,wecansimplifyittoincludealltheseinanewrateconstant:
,
p y

k isoftencalledtheobservedrateconstant(k
k
is often called the observed rate constant (kobs)
Ifwetakethelogarithmofr,weget

Measuringtheinitialrateofthereactionasafunctionoftheinitial
concentrationofA,[A]0,andplottinglogd[A]/dt vs.log[A]0,givesthe
reactionordera ofreactantA astheslopeandlogk astheyintercept
Onlytheratedeterminingstepmaybedirectlymeasuredbytraditional
means

FormationConstants(thermodynamics)
Keq =

[L][(ML5L')m+]
[L'][(ML6)n+]

= Kf

N.B.thesquarebrackets[]hereimply
concentrationoftheionorligand

IfLisasolvent(e.g.anH20ligand inaqueoussolution),theconcentration
ofL,[L]isignoredbecauseitsconcn doesnotchangeindilutesolutions
IfKf islarge,theincomingligand bindsstrongly(strongerthansolvent)
IfKf issmall,theligand bindsweakly.
BecauserangeofKf valuesishuge,theyareoftenexpressedaslogKf
More than one ligand maybereplaced(e.g.[Ni(OH
Morethanoneligand
may be replaced (e g [Ni(OH2)6]2+ to[Ni(NH
to [Ni(NH3)6]2+)
Thereareuptosixsteps,evenifweignorecistrans isomerization,and
eachstephasitsownformationconstant!Yuck!
But these stepwise formation constants yield information about
But,thesestepwiseformationconstantsyieldinformationabout
structureactivityrelationships(SAR)
Itsoftendifficulttoobserveeachstepindividually,andinsteadweobtain
an overall formation constant n,whichincludesthensteps.
anoverallformationconstant,
which includes the n steps
n =Kf1Kf2Kf3Kfn
4

Generally,theK
Generally,
the Kf ofeachstepdecreaseswitheachligand
of each step decreases with each ligand swapped(Table20.2)
swapped (Table 20.2)
IfKf increasesforthenextligand added,thisimpliesamajorchangeinthe
electronicstructureofthecomplex(e.g.ongoingfromhighspintolowspin)
and therefore a big increase in LFSE.
andthereforeabigincreaseinLFSE.
[Fe(H2O)6]2+ +3bipy [Fe(bipy)3]2+ +6H2O
[Fe(bipy)2(H2O)2]2+ (hs d6)vs.[Fe(bipy)3]2+ (ls d6)
Thi
Thisexamplealsoexperiencesachelate
l l
i
h l t effectonthethermodynamics(an
ff t
th th
d
i (
entropiceffect,butmoreonthatlater)

SubstitutionReactionsinOctahedralcomplexes

EExchangeone(ormore)ligand(s)foranother,e.g.theweakerligand
h
(
) li d( ) f
th
th
k li d H2Ofora
Of
thestrongerdonorNH3:

Thedifferentligand fieldstrengthsmeandifferentO,thereforepotentially
different colours. Can follow by photometric determination(i.e.UV
differentcolours.Canfollowbyphotometric
determination (i.e. UVvis).
vis).
Whichismorestable?[Cu(H2O)6]2+ isstableinwater,butunstablew.r.t.
formationofamminecomplexinpresenceofaqueousNH3,(i.e.ithasalargeKf)
How fast is the reaction (i e is it labile or inert?) An inert complexreactsslowly,
Howfastisthereaction(i.e.isitlabileorinert?)Aninert
complex reacts slowly
eveniftheKf liestotheright(tothethermodynamicallyfavoured product)and
hashighactivationenergy(Ea).Labile complexeshavelowEa andreactfast(t1/2
<1minute).NowneedKINETICclassification,notjustTHERMODYNAMIC.
1 minute). Now need KINETIC classification, not just THERMODYNAMIC.
Canwepredictlabilevs.inert?Yes!HighLFSEcomplexesaregenerally inert
(someexceptions).

Ligand ExchangeisaNucleophilic Substitution

Thelability orinertness(ornonlability asS&Ainsist)ofsubstitutionreactions

dependsonboththemetalionandtheligand (Duh!)andalsosolventchoice
Fordblockions:
Inert:d3;l.s.d4,d5,d6;sq.pl.d8
Labile:d1;d2;h.s.d4,d5,d6;d7;d9;d10
Intermediate:weakfieldd
Intermediate: weak field d8 (e.g.Ni
(e g Ni2+ withweakfieldligands)
with weak field ligands)
Sblockionsarelabile(exceptforthesmallest,Be2+ andMg2+)
M(III)fblockionsarelabile
M(II)dblockionsaremore
( ) d bl k i
labilethanM(III)ions
4d and5dmetalsaremore
i
inertthan3dcongeners
h 3d
Ratedependson
nucleophilicity ofincoming
li d d bili
ligand,andabilityoftheMto
f h M
createavacantsite

Fig.20.2p496

ClassificationofSubstitutionMechanisms

Theratedeterminingstepinoctahedralcomplexescanbeoneofthree:
Dissociate(D),Associative(A)orInterchange(I)
Dissociative:lossofoneligand beforenewligand binds,leadingtoa
potentiallyisolableintermediate
Associative:gainofaligand leadstoahighlycoordinatedintermediate
followedbydisplacementofaweaklyboundligand
Interchange:Norealintermediate.Rateofligand lossandnucleophilic
attackarenearlyidentical

DissociativeMechanism(Dtype)
Typicalfor6coord.complexes
CO
OC

CO
CO

W
OC

CO

CO

CO

CO

CO

PPh3

OC

OC

CO

+ CO

CO
W

OC
CO

W
OC

CO

OC

OC

PPh3
CO

Intermediatescanbestabilizedbydonorsolvents.SolventslikeTHFaregood
Lewisbasesthatcanactasplaceholdersgivingsolvento complexes.
Ligand lossmayneedtobeencouragedviaanexcitedstate.Wisl.s.d6 (inert)so
(
)
thereactionisSLOWunlessheated orphotochemically inducedbyputtingane
intoaneg*orbital(i.e.t2g6 t2g5eg1),whichismorelabile.
Leavinggroupeffectsareimportant,aswellasnucleophile
ff
ll
l
h l strengthofnewL
h f

RatelawsforDmechanisms
ML5X

k1
k-1

ML5 + Y

ML5 + X
k2

ML5Y

d[ML5]
dt

[ML5] =

rds

= k1[ML5X] - k-11[ML5][X] - k2[ML5][Y] = 0

k1[ML5X]
k-1[X] + k2[Y]

][Y]] =
d[ML
[ 5Y]] = k2[[ML5][
dt

Sincek1 <<k2,andtheaccumulationofthe
intermediateML5 maybehamperedbythereverse
reaction,therateoftheoverallreactionwill
d
dependontherateofformationofML
d
th
t ff
ti
f ML5
Steadystateapproximationassumestheconcn of
ML5 will,therefore,besmall(assoonasitis
formed,itisattackedbyeitherYorX)
y
)
Weexpresstheoverallrateofreactionintermsof
rateofformationofML5:

Solvefor[ML5]andsubstituteintotheratelawfor
p
g
theformationoftheproductgivestheoverallrate
lawforthereaction.
k2k1[[ML5X][Y]
][ ]
k-1[X] + k2[Y]

**Remember,forthismechanismtobetrue,the
intermediateML5 mustbedetectable.Because
di t d t ti
directdetectionatthelowconcentrations
t th l
t ti
expectedisexperimentallydifficult,thereare
fewclearcutDmechanisms.Iftheintermediate
cantbedetected,itwouldbeclassifiedasId

10

AssociativeMechanism(Atype)
Typicalforfour
yp
orfivecoordinatecomplexes
p

Mostcommonforfour orfivecoordinatecomplexes(esp.sq.planar)
Alreadyhasanemptysite!PrimarilydependsonLnucleophilicity.
14

NC

CN

2-

Ni
NC

14

CN-

3CN
-CN-

NC
Ni

CN

CN

2-

Ni

CN
NC

NC

14

NC

CN

CN

Forsq.planarlatemetalcomplexes(Pd
For
sq planar late metal complexes (PdII,Pt
PtII,Ir
IrI)therateincreasesfor
) the rate increases for
strongnucleophiles andstrongacceptors
H2O<Cl <I <H <PR3 <CO,CN
Th f
Thereforegoodleavinggroupsareligands
dl i
li d thatarepoorernucs
th t
leadingto
l di t
atrans effectandtrans influence(kineticandthermo,respectively)
Moreontrans effectandinfluencelater(v.importantforstereoselectivity
l di t
leadingtowardcis
d i vs.trans
t
i
isomers)
)
11

RatelawsforAmechanisms
Thefirststepdependsontheincomingligand,Y,
andistherds
k1
Lossofaligand insecondstepisfast
ML5X + Y
ML5XY rds
Steadystateapproximationassumestheconcn
St d t t
i ti
th
of
f
k-1
ML5XYwill,therefore,besmall
k2

Weexpresstheoverallrateofreactionintermsof
ML5XY
ML5Y + X
rateofformationofML5Y:
d[ML5Y]
dt

k2k1[ML5X][Y]

= kobs[ML5X][Y]

k-11 + k2

Theseparaterateconstantscannowbecombinedintoasingleobservedrate
constant,kobs.
As expected the rate law is second order and depends on the concentration of
Asexpected,theratelawissecondorderanddependsontheconcentrationof
bothreactants.
**AswithDmechanisms,thereareveryfewclearcutexamplesAmechanismsinwhichthe
intermediate is detectable Most reactions fit between the two extremes following interchange
intermediateisdetectable.Mostreactionsfitbetweenthetwoextremes,followinginterchange
mechanisms.Iftheintermediatecantbedetectedbutthereisadependenceontheincomingligand,
itwouldbeclassifiedasIa

12

InterchangeMechanism(Itype)

Sortofanassociativetypebutcommonforsixcoordinatecomplexes
Nodetectableintermediatesinceassociationanddissociationoccurinonestep
l di t hi h
leadingtoahighenergytransitionstate
t
iti
t t
Thereisalsoasubtledistinctionbetweenadissociativeinterchange(Id)andan
associativeinterchange(Ia)

Basically,ifyoucanobserveanintermediatespectroscopically
Basically
if you can observe an intermediate spectroscopically (dependingon
(depending on
therateyoucoulduseNMR,UVvis consideringspectroscopictimescales)the
mechanismwillnotbeinterchange.
Not easy to nail down the rds sohavetovarymanyconditionsandstudytheir
Noteasytonaildowntherds
so have to vary many conditions and study their
effectsonrate(andstereochemistry!)
13

Figs.20.320.5

Dissoc.

ReactionProfiles

Assoc.

Interchange

Howdoyoudeterminewhichmechanismoccurs?
A:ratedependsstronglyonincomingligand
d
d
l
i
i li d (likeS
(lik SN2),strongernucleophiles
2)
l
hil
givefasterrates.
D:rateisindependentoftheincomingligand (likeSN1).Ifchangingthe
i
incomingligand
i li d haslittleeffectonrate,therds
h li l ff
h d isdissociative.
i di
i i

14

Twostudies
NH2

HN Pt
NH2

NH2

NH2
Cl

+ I

HN Pt

+ Cl

NH2

HN Pt

NH2
-

Cl + Br

NH2

HN Pt

Br

+ Cl-

NH2

A is~102 xfasterthanB.I isabetternucleophile thanBr.AnAssoc.rds.

The tridentate ligand iscalled
Thetridentateligand
is called dien
dien (diethylenetriamine)andbecauseitisa
(diethylenetriamine) and because it is a
chelatingligand,itisstronglyboundtothemetal(moreonchelate effect)

A [Ni(H2O)6]2+ + NH3

[Ni(H2O)5(NH3)]2+ + H2O

B [Ni(H2O)6]2+ + Py
P

[Ni(H2O)5(Py)]
(P )]2+ + H2O

A andB havealmostthesameratesofreactiondespitepyridinebeingamuch
strongernucleophile.Therds mustbedissociative.

15

ProbingtheMechanism

So,wecanhavearangeofdetailedmechanisms
A
Ia
I
Id
D
Studyingthemechanismmayinvolvealteringthephysicalconditions(T,P,
solvent)butthismaycomplicatematters
Often,trendscanbeobtainedbyfinetuningtheligand.Mostusefulare
NR3 andPR3 ligands,whereRgroupsareeasilychangedtovarythe
nucleophilicity ofthedonoratomwithoutaffectingthesterics toomuch.
Forsystemswherenointermediateisobservable(anImechanism),the
rds maybeeitheraord(associativelyactivatedordissociatively activated,
seep.499inS&A)
Computationalchemistryishelpfulforpostulatingtherelativeenergiesof
possiblereactionintermediatesandtransitionstates,butofcoursethese
hypothesesmustbesupportedbyother(evenifindirect)methods
Finally,youcanneverprovethatyourmechanismisright.Youcanonly
disproveit.
16

TheChelate Effect

Chelatingligands (en,bipy,dppe)affectboththermodynamicsandkineticsof
areaction
+ thousands more
R2N

NR2

R2P

If R = Ph, 1,2-bis(diphenylphosphino)ethane,
dppe (or diphos)
If R = Me,
M 1,2-bis(dimethylphosphino)ethane,
1 2 bi (di th l h
hi ) th
dmpe

2,2' bipyridine,
If R = H, ethylenediamine, en
If R = Me,, tetramethylethylenediamine,
y
y
, bipy (or dipy)
TMEDA

[M(NH3)4(en)]2+ + 2 NH3

[M(NH3)6]2+ + en

PR2

Netincreaseinproductmoleculesvs.reactants entropiceffect
Considerthefollowingdataforformationof[Cd(CH3NH2)4]2+ vs.[Cd(en)2]2+ at
298K
298K
Ligand

-TS kJ/mol G kJ/mol

H kJ/mol

S J/molK

4 CH3NH2
4CH

57
57.3
3

67
67.3
3

+20 1
+20.1

37
37.2
2

2en

56.5

+14.1

4.2

60.7
17

TranseffectandTransinfluence
Mostpronouncedinsquareplanarcomplexes(butfoundinoctahedralalso)
Spectatorligands,T,(thosenotundergoingexchange)transtotheleaving
groupaffecttherateofdisplacement(transeffect)orstrengthofthebond
(transinfluence) oftheleavinggroup,X.
Strongdonor/acceptorligands acceleratetherateofsubstitution
p
g
basedon and bondingg
S&A4E:p.503inthetextranksligands
Hereisanoveralltrendfromweakesttostrongest:
F,H2O,OH <NH3 <py <Cl <Br <I,SCN,NO2,SC(NH2)2,Ph <SO32
< PR3,AsR
<PR
AsR3,SR
SR2,CH
CH3 <H
< H,NO,CO,CN
NO CO CN,C
C2H4
ThegreatertheMToverlapthestrongertheeffect(C=cis ligand,Y=
nucleophile,T=strongTranseffectligand,X=leavinggroup

C
X

T
Y

Y
C

18

Alookatrateconstants,k

Strong trans effect

Strongtranseffect
Weaktranseffect
Verystrongtranseffect

19

Steric Effects

Transinfluenceraisesthegroundstateoftheinitialcomplex(thermodynamics)
Transeffectmakestheleavinggroupmorelabile(kinetics)
Ligands cis toleavinggrouphavelittleinfluence,exceptwhensterically bulky
Largeligands canpreventAssociativereactionsandfavour Dissociativerds
Insquareplanarsystemsthisslowsdowntheligand exchangeandimproves
kineticinertness
PEt3
N

Pt

PEt3

k = 8x10-2 s-1

Cl
PEt3
N

Pt

PEt3 k = 1x10-6 s-1

Cl

20

InfluenceonEa andG.S.Energy
Ea
Ea

G.S.

Ea

G.S.

G.S.

21