Questions&AnswersonCoordinationChemistry(DRay)

[Link]?
(i)[AlCl4]
(ii)[Ag(NH3)2]+
[Link],linear

[Link],coordinationnumber,andthe
overallchargeonthecomplexioninNH4[Cr(NH3)2(NCS)4]?
Ans.+3;6;1

3. The formula for lithium iodotris(trifluorophosphine)nickelate(0) is: (Note:

[Link],F,orCN?
Ans.F

[Link]:K2[CrCO(CN)5].
[Link](III)

[Link]?
Ans. Macrocyclic ligands of appropriate size form more stable complexes than chelate
ligands. A competition between a noncyclic chelating ligand and a macrocyclic
(chelating)ligandhavingthesamenumberandtypeofdonoratomswillgenerallylead
to complex formation predominantly by the macrocyclic ligand. This is known as the
macrocycliceffect.

[Link]
more flexible than the corresponding macrocyclic ligand and can adopt many more
conformationsthanthemacrocyclicligandwhenitisnotcoordinated.

7. Predict the no. of unpaired electrons, the spinonly magnetic moments at 25 C for

eachofthefollowing.
a)[Fe(CN)6]4
b)[Ru(NH3)6]3+
c)[Cr(NH3)6]2+
d)[EuCl6]4
Ans. a) Fe2+ is 3d6. Has 0 unpaired electron in l.s. complexes and thus the magnetic
momentwouldbecloseto0B.
b)Ru3+[Link]
wouldbecloseto1.73B.
c) Cr2+[Link] [Link]
magneticmomentwouldbecloseto4.90and2.83B,respectively.
d)Eu2+[Link]
[Link]
only values because of strong spinorbit coupling. The forbitals have so little overlap
andinteractionswithligandorbitals.

8. With reference to the 3d elements in the periodic table identify the elements and
associated oxidation numbers that form square planar complexes. Give formulas for
threeexamplesofsuchcomplexes.
Ans. The squareplanar geometry is primarily associated with the d8 electron
configuration, and the following elements and oxidation states commonly form the d8
configuration:
3456789101112
Ni2+
Rh+Pd2+
Ir+Pt2+Au3+

Examplesofsuchcomplexes:RhCl(PPh3)3,IrCl(CO)(PPh3)2,Ni(CN)42,PdCl42,cisand
transPtCl2(NH3)2 and AuCl4. Note however that NiCl42 is not square planar, but is
[Link],[Link]
withincreasingligandfieldstrength;theligandfieldsforthe2ndand3rdtransitionseries
are intrinsically larger than for the first series metals. Note however, that Ni(CO)4 is
alsotetrahedral,notsquareplanar,butthatisbecausethiscomplexisd10,ratherthan
d8!

9. Sketch the two structures that describe most sixcoordinate complexes. Which is
morecommon?
[Link]

Hexamminecobalt(III)chloride

Trigonalprismaticisanextremelyraregeometry,butoctahedralisextremelycommon.

10. The compound Na2IrCl6 reacts with triphenylphosphine in diethylene glycol under
an atmosphere of CO to give trans[IrCl(CO)(PPh3)2], known as Vaskas compound.
Excess CO produces a fivecoordinate species and treatment with NaBH4 in ethanol
gives[IrH(CO)2(PPh3)2].Drawandnamethethreecomplexes.
Ans.

Names,inoder:Carbonylchlorobis(triphenylphosphine)iridium(I),
Dicarbonylchlorobis(triphenylphosphine)iridium(I),and
Carbonylhydridobis(triphenylphosphine)iridium(I).

11. Which of the following complexes are chiral? (a) [Cr(ox)3]3; (b) cis[PtCl2(en)]; (c)
cis[RhCl2(NH3)4]+; (d) [Ru(bipy)3]4+; (e) [Co(edta)]; (f) fac[Co(NO2)3(dien)]; (g) mer
[Co(NO2)3(dien)].Identifytheenantiomersaschiralandachiralcomplexes.
Ans. (a) [Cr(ox)3]3 It is definitely chiral; two chelating ligands on an octahedral
framework are sufficient do impart chirality to the complex. The two enantiomers
providetheleftandrightofaplaneofreflection.
(b)cis[PtCl2(en)]Thismoleculewouldbechiralbecauseofthetwistintheenligand.
However, ring inversion in chelate complexes of this type (as in cyclopentane) is very
fastatroomtemperatureandwellbelow,sothatenantiomerscannotbeisolated,and
thecomplexisnormallyconsideredtobeachiral.
(c)cis[RhCl2(NH3)4]+Thiscomplexisachiral.IthasC2vsymmetry,andthushastwo
internal mirror planes, which can be clearly seen in the picture of the molecule, one
[Link]
ammine ligands to be in a specific orientation. In practice, the RhN bonds rotate
sufficiently fast that the ammine ligands are effectively spherical, so the molecule
definitelyactsasaC2vspecies.

(d)[Ru(bipy)3]4+Thisisanotherexampleofatrischelatecomplex,andthereforewillbe
both chiral and easily resolvable. The stucture is shown with its nonsuperimposible
mirrorimagebelow(Hatomsomittedforclarity).
(e) [Co(edta)] When EDTA chelates a metal such that all six donor atoms coordinate
(themostcommon,butnottheonlywaythatthisligandattachestometals)thenthe
[Link]
inthesystem.
(f)fac[Co(NO2)3(dien)](notetypoinquestion!)and(g)mer[Co(NO2)3(dien)].Ifone
ignores the conformations of the chelate rings, the complexes are not chiral. The
chelates are ethylenediamine linkages, and as discussed for (b) above, such rings
[Link]
facialisomerhasaninternalplaneofsymmetrythatincludesthecentralNofdien,the
[Link]
ligand and the metal (as well as one through the metal and the three nitro N atoms.)
Theseplanesareverticaltothepaperthroughthemiddleofthemolecules.

12.WhatisthecoordinationnumberoftheFeatomisK3[Fe(C2O4)3]?
[Link]
thecentralmetal,3x2=6.

[Link][Au(CN)2(SCN)2]?
[Link]
tothecentralmetal.

[Link]?
NH3,C2O42,CO,OH
Ans.OnlyC2O42,oxalate,[Link].

[Link](EDTA4)iscommonlyreferredtoasa
___________ligand.
[Link]

[Link]
followingcoordinationcomplexes:
a)[CoCl4]2;b)[Fe(bpy)3]3+;c)[Cu(ox)2]2;d)[Cr(CO)6]
Ans.a)EachClligandhasachargeof1,so4x1=4
Overallchargeonthecomplexis2,sotheoxidationstateofCo=+2.
GroundstateconfigurationforCo=[Ar]3d74s2

Onlossof2e,Co2+hasconfiguration[Ar]3d7,sosevendelectrons.

b)bpy(2,2Bipirydyl)isuncharged=neutral
OxidationstateofFe=+[Link]=[Ar]3d64s2
Onlossof3eFe3+hasconfiguration[Ar]3d5,sofivedelectrons.

c)ox(oxalate,C2O42)hascharge2peroxalate,sototal=2x2=4
Overallchargeoncomplex=2,sotheoxidationstateofCu=+2.
GroundstateconfigurationforCu=[Ar]3d104s1
Onlossof2e,Cu2+hasconfiguration[Ar]3d9,soninedelectrons.

d)COisuncharged=neutral.
OxidationstateofCr=[Link],allelectronsarein3dorbitalswhicharenowof
lowerenergy(becausefilled)[Link]=[Ar]
3d54s1.ConfigurationforCr0=[Ar]3d6,sosixdelectrons.

[Link]:
a)transdiaquadichloroplatinum(II)
b)diamminetetra(isothiocyanato)chromate(III)
Ans.a)

H2O(aqua)[Link]=1.
[Link]+2oxidationstate
sothecomplexisuncharged.TransindicatedthattheClandH2Oligandsarelocated
oppositeeachother.

b)

AmmineisNH3,[Link]=SCN,which
[Link](III)indicates

that this is an anion with Cr in the 3+ oxidation state. Charge on SCN = 4 x 1 = 4.

[Link](II)complexexplainthefollowingelectronicspectrumwiththehelpof
theadjacentTanabeSuganodiagram.

[Link]
intheUVandvisibleelectromagneticspectrumofcoordinationcompounds.
It can be used to assign transitions for the absorptions. The first peak is due to the
4
A2g(F)4T2g(F)[Link]
4
A2g(F)4T1g(F)transition.Thethirdpeakisduetothe4A2g(F)4T1g(P)transition.

[Link].
Ans. In atomic physics, Hund's rules refer to a set of rules formulated by German
physicist Friedrich Hund around 1927, which are used to determine the term symbol
[Link],ruleoneis
especiallyimportantandisoftenreferredtoassimplyHund'srules.
Thethreerulesare:
1) For a given electron configuration, the term with maximum multiplicity has the
lowestenergy.Sincemultiplicityis2S+1equalto,thisisalsothetermwithmaximumS.
Sisthespinangularmomentum.
2) Foragivenmultiplicity, thetermwith the largest value of L has thelowest energy,
whereListheorbitalangularmomentum.
3)Foragiventerm,inanatomwithoutermostsubshellhalffilledorless,thelevelwith
[Link],
[Link],J=

L+S.

[Link][Cu(H2O)6]2+.
[Link](JT)theoremstatesthatinmolecules/ionsthathaveadegenerate
groundstate, the molecule/ion will distort to remove the degeneracy. This is a fancy
wayofsayingthatwhenorbitalsinthesamelevelareoccupiedbydifferentnumbersof
electrons,[Link],whatisimportantisthatif
thetwoorbitalsoftheeglevelhavedifferentnumbersofelectrons,thiswillleadtoJT
[Link](II)withitsd9configurationisdegenerateandhasJTdistortion.

21. Why the magnetic moment of an octahedral monothiocarbamate complex of Iron

[Link]?
Ans:Thecomplexanionsuchas[Ni(CN)5]3canbecrystallizedusingsolubilitytendency
by adding a large counterion of opposite charge. Five coordinate [Ni(CN)5]3 ion
prevented
isolation
from
solution
until
the
matched
counterion
3+
[Cr(NH2CH2CH2NH2)3] was added, whereupon [Cr(en)3][Ni(CN)5].15H2O crystallized
[Link]
not dissolve the product (e.g., adding EtOH to the aqueous solution) can help to
crystallizeasaltoftheproduct.


23.HowwillyouprepareK3[Rh(ox)3]fromkineticallyinertK3[RhCl6]?
K+
100C
Ans:[RhCl6]3+3ox2
[Rh(ox)3]3

Winered2hYellowEvaporation
With kinetically inert starting complex, the reaction requires boiling in some high
boiling solvent for some hours followed by the supply of appropriate (matching)
counterion.

[Link][Cr(en)3]Cl3frominert[Cr(H2O)6]Cl3?
Ans:[Cr(H2O)6]3++3en
[Cr(OH)3(H2O)3](s)+3enH+
Iftheligandisbasicinwater,andthemetalionisappreciablyacidicaswellasbeinga
hardacid,themetalionmayprefertoreactwiththehydroxideionsgeneratedbythe
ligandinwater,ratherthantheliganditself.
d3 Cr3+ ion is inert and the water molecules do not dissociate as quickly as the basic
liganddeprotonatestheacidiccoordinatedwatermolecules.

dryEt2O
[Cr(en)3]Cl3
CrCl3(anhydrous)+3en

Yellow

[Link].
Ans: Volatile ligands such as CO, H2O or NH3 are driven off by heating and then are
replacedbyadesiredligandinsolutionorbythecounterionsofthestartingcomplex.
250C
trans[PtCl2(NH3)2]+2NH3(g)
[Pt(NH3)4]Cl2(s)
White
hPPh3
CO(g)+W(CO)5
[W(CO)5(PPh3)]
[W(CO)6]
reactiveunsaturated
complex

[Link]?
Ans: Macrocyclic ligands of appropriate size form more stable complexes than chelate
ligands. A competition between a noncyclic chelating ligand and a macrocyclic
(chelating) ligand having the same no. and type of donor atoms will generally lead to

complex formation predominantly by the macrocyclic ligand. This is known as the

[Link]
more flexible than the corresponding macrocyclic ligand and can adopt many more
conformationsthanthemacrocyclicwhenitisnotcoordinated.

[Link],themagneticmomentsat25Cforeachof
thefollowing
(a)[Fe(CN)6]4,(b)[Ru(NH3)6]3+,(c)[Cr(NH3)6]2+,(d)[EuCl6]4.
Ans:(a)[Fe(CN)6]4Fe2+3d6.
Lowspincomplex0(zero)unpairedelectronB=0

(b)[Ru(NH3)6]3+Ru3+4d5.
LowspincomplexoneunpairedelectronB=1.73BM.

(c)[Cr(NH3)6]2+Cr2+3d4.
Highspincomplex4unpairedelectronsB=4.90BM.
Lowspincomplex2unpairedelectronsB=2.83BM.

(d)[EuCl6]4Eu2+4f7.
Highspincomplex7unpairedelectronsB=7.9BM.
Theforbitalshavesolittleoverlapandinteractionwithligandorbitals.

28.Amongthefollowing3dtransitionmetalionswhichoneiskineticallyinert?
Cr2+,C03+,C02+,Fe3+
Ans.C03+

[Link]
ofanysquareplanarcomplexiscorrect?
[Link],whereasthetranseffecthasakinetic
origin
[Link],whereasthetransinfluencehasakinetic
origin

[Link]
[Link]
Ans.[A]

[Link]:
[Link]
[Link]
[Link]
[Link]
[Link].

[Link][Mn(H2O)2(ox)2]2.
Ans.H2Oismonodentateandoxisbidentateoxalateionandrepresentedby

[Link]
morecommon?
Ans.

Incoordinationchemistrytrigonalprismaticisararegeometry,butoctahedralis
extremelycommon.

[Link]
coordinatestructure.
[Link][Cr(NH3)6]3+,[Cr(CO)6],
[Cr(OH2)6]2+,[Fe(CN)6]3,[Fe(CN)6]4,and[RhCl6][Link],almostallmetal
aquaions(saveonlyCu2inthefirstTMseries)haveoctahedralaquacomplexesinwater
ordiluteacid.

[Link]:(a)[Ni(CO)4];(b)[Ni(CN)4]2;
(c)[CoCl4]2;(d)[Ni(NH3)6]2+.
Ans.

35. Determine the configuration (in the form t2gmegn or emt2n, as appropriate), the
numberofunpairedelectrons,andtheligandfieldstabilizationenergyasamultipleof
oorTforeachofthefollowingcomplexesusingthespectrochemicalseriestodecide,
where relevant, which are likely to be strongfield and which weakfield.
(a)[Co(NH3)6]3+; (b) [Fe(OH2)6]2+; (c) [Fe(CN)6]3; (d) [Cr(NH3)6]3+; (e) [W(CO)6]; (f)
[FeCl4]2and(g)[Ni(CO)4].

Ans.(a)[Co(NH3)6]3+
Since the NH3 ligands are neutral, this is a Co3+ complex, so we are dealing with a d6
[Link],ametalin
the3+oxidationstateispastthemiddleofthemetalseries,sothecombinationisvery
likely to be a lowspin configuration, t2g6eg0. Indeed, octahedral d6 has S = 0 (no
unpairedelectrons)andisdiamagnetic.TheLFSEis60.4o=[Link]
thelargestpossibleLFSEforanoctahedralcomplex.

(b)[Fe(OH2)6]2+
The iron ion in this octahedral complex with six neutral water ligands is in the 2+
oxidationstate,[Link]
d6iontobeinahighspinconfiguration,t2g4eg2,withS=[Link],ithasfourunpaired
electronsandisstronglyparamagnetic.TheLFSEis40.4o20.6o=0.4o.
NotethemuchsmallerLFSEcomparedtothelowspind6casediscussedin(a).

(c)[Fe(CN)6]3
The iron in this octahedral complex with six 1 cyanide ligands is in the 3+ oxidation
state, and cyanide is high on the spectrochemical series. This is almost certainly a
complex with a low spin configuration. Fe3+ is a d5 metal ion, and hence the
configurationwillbet2g5eg0,withS=.TheLFSEis50.4o00.6o=2.0o.

(d)[Cr(NH3)6]3+
Thecomplexcontainssixneutralammonialigands,soitisCr3+,whichisad3metalion.
Thereisonlyoneelectronconfigurationforoctahedrald3,i.e.t2g3eg0,whichmeansthat

therearethreeunpairedelectronsandS=3/2.TheLFSEis30.4o00.6o=1.2o.

(e) [W(CO)6] Carbon monoxide is neutral and is very high on the spectrochemical
[Link].
However,inthecomplexwepromotethe4selectronsinto3d,sothatitisnonethelessa
[Link],withconfigurationt2g6eg0,andS=[Link]
LFSEis2.4o.

(f)[FeCl4]2
Thisisatetrahedralcomplex,becausetheligandsare1,themetalistherefore2+,and
Fe2+ is d6, which is not a candidate for square planar geometry. Remember that all
tetrahedralcomplexesarehighspinbecauseTisinherentlysmall{T=(4/9)o}.Thus
theexpectedelectronconfigurationise2t23,andS=2.0forfourunpairedelectrons,and
stronglyparamagnetic.TheLFSEis30.6T30.4T=0.6T.

(g)[Ni(CO)4]
This is also a tetrahedral complex, because the ligands are neutral, the metal is (after
promotion of the 4s electrons) d10, and hence not a candidate for square planar
[Link],regardlessofgeometry,complexesofd10metalatomsandionswill
alwayshaveLFSE=0,andthiscomplexisnoexception.

[Link][PtCl2(NH3)2]wasidentifiedasthetransisomer.(The
cis isomer was denoted .) It reacts slowly with solid Ag2O to produce
[Pt(NH3)2(OH2)2]2+.Thiscomplexdoesnotreactwithethylendiaminetogiveachelated
[Link].
[Link]
thetransisomer,sincethischelatingligandcannotstretchacrossametaltooccupytwo
transpositionsonanymetalion;[Link]
thustransdiamminediaquaplatinum(II):

[Link](neithernor,seepreviousquestion)ofcompositionPtCl22NH3
is an insoluble solid which, when ground with AgNO3, gives a solution containing
[Pt(NH3)4](NO3)2andanewsolidphaseofcompositionAg2[PtCl4].Givethestructures
andnamesofeachofthesePt(II)compounds.

[Link][Pt(NH3)4][PtCl4],andthisfits
theobservedreaction:
[Pt(NH3)4][PtCl4]+2AgNO3[Pt(NH3)4](NO3)2+Ag2[PtCl4](s)

[Link]?
Ans. If the metal is in a low oxidation state and the ligand possesses lowlying empty
orbitals(forexampleCOorCN)[Link]
anelectronfromthet2g(pi)andtheeg(sigma*)tothet1u(pi*/sigma*).Thesetransitions
arise from pi acceptor ligandsand metals thatarewilling to donate electrons into the
orbitals of Ligand character. Examples of pi accepting ligands are as follows: CO, NO,
CN,N2,bpy,ophen,RNC,C5H5,C=Cbondedgroups,CCbondedgroups.

MetaltoLigandChargeTransfer(MLCT)involvinganoctahedrald5complex.

39.[Cu(H2O)6]2+and[Cu(NH3)4]2+bothappearblueinsolutionbecauseofthepresence
of copper ions. However, the two solutions are not [Link] would the
appearance of these solutions differ? If given an unlabeledsample of each, how could
thetwosolutionsbedistinguishedwithoutcollectinganyspectra?
Ans.[Cu(NH3)4]2+[Link]
it is noncentrosymmetric, it is not Laporte forbidden. [Cu(H2O)6]2+is an octahedral
complex whose dd transitions are Laporte forbidden. [Cu(NH3)4]2+will be a darker
shade of blue in solution because its dd transitions are not forbidden, and
[Cu(H2O)6]2+will have a pale shade of blue in solution because its dd transitions are
Laporte forbidden. Coloration and absorption of[Cu(H2O)6]2+in the ultravioletvisible
rangeisattributedtovibroniccoupling.

[Link]?
Ans. SQUID is superconducting quantum interference device. The superconducting
quantum interference device (SQUID) consists of two superconductors separated by
thin insulating layers to form two parallel Josephson junctions. The device may be
configuredasamagnetometertodetectincrediblysmallmagneticfieldssmallenough
[Link]
themagneticfieldsinmousebrainstotestwhethertheremightbeenoughmagnetism
toattributetheirnavigationalabilitytoaninternalcompass.
The great sensitivity of the SQUID devices is associated with measuring changes in
[Link]
[Link]
maintained in the SQUID device, the measured voltage oscillates with the changes in
phase at the two junctions, which depends upon the change in the magnetic flux.
Countingtheoscillationsallowsyoutoevaluatethefluxchangewhichhasoccurred.