Coordination

Compounds 9
Section-1
1. Write the formulas for
coordination compounds :
(i) T•traamminediaquacobalt(llll chlorid•
(ii) Potassium tetracyanidonickelate(IO
(Iii) Tris(ethan<-1,2-diamine) chromium(III)
chloride
(iv) Amminebromidochloridonltrito•N·
platinat,(11)
(v) Dichloridobis(ethane -T,2-diamln•J
platinum(IV) nitrate
(vi) lron(IIIJ hexacyanidoferrate(lll
mill (i) /Cc,(N H,).( H,0), JCI,
(ii) K:fNi(CN), I
(,ii) /Cr(m), /Ch M irrpr

(iv) fPt(NH,)BrCl(NO,)I
(v) /PICl,(e11),[NO,),
(vi) Fe, ffr(CN), b
2. Write the IUPAC names of the following
coordination compounds :
(i) {Co(NH )JCl (ii) [Co(NH, J, Cl)CI,
3 3
(iii) K, [Fe(CNJJ (iv) K3 [Fe[C20 ,J, l
M irror
(v) K, [PdCl, J
(vi) [Pt(NH,J,Cl(NH, CH, )JCI
(iii) Ion iza tion i!-om t: rc,; :
mill (i) J-lexaammi necoba lt(III) chlo rid e {Co(NH, ), (NO,JJ (NO ,),
(ii) Pen taa mm inl"chlondofob.ilt(Jl l)ch/orid l' _ /Co(N H,J, (NO,J/(NO,J(NO
(iii) Potassn1111 hL-x..1cya nidoferrate(III) Linkage ,so m e rs · {Co(N H , ;l
[Co(N f-1 , )s (ONO) j(NO ,J , ),(NO,)/(\() ,
(iv) Potas!>ium trioxalatoferr.ite( III )
(v) Potassiu m lC' tr.1chloridopJJI JdJlt'(ll ) (i~) Gt:ometrical (r"is- , ;,,,,,.,_)
t' \.I St. jli(')Tnt l°'I
(vi) Di.:Jmmmcchlorido (mdhyJami ne)
1-1,__~-s;,··------- ---·:_:;;;--:,Cl H,N ,.,,
platinum (ll) chl ori dl'
3. Indicate the types of isomerism exhibite d
'--.. / i~ ·-- .(
by the following complexes and draw the H,O~-l~-1-~C- I _.' _,-- P t ~
structures for these isomers :
~ c,~ --- · -".,
(i) K{Cr(H,O), (C 2O, J,] (ii) [Co(en),JCI,
V

hl\{1 ComPounds
,# II'". 155
c•~ vidence t~at . [C~(N~3)sC1Jso. and
i.e e soJCI are ,omsat,on isomers. presence of H O (
do . . 1 , a we,1k ligand), Ji/ c ledron~
G uH ls · · . fo n_o t p,11r up. 'The hybridisiltion is s1rld2
A· ico{•• i 1'h•· i,H11 s,'.t1nn 1,omcrs di,so)vp in
' l complt>x con tammg
fi rm1n g an ou t-l'r o r b 1ta ..
t<l ,. iclJ diHNC'nt wns and thus re~ct
,,-.it~r II' 10 variou s re.igcnts: vt> unpairrd clf•ctroos hence, it is st rong ly
pa ra magne tic.
Ji~,J•'ntl, Cl]S04 + 8a2• -> BaSO~c-1(whitc ppt.)
,(,~,r,1t1 ,l, SO ]Cl +- Bd ." ·-+ No reaction
·
S.
I r,.:!1 ,' • Ex.;fain [Co(NH3).P • is an inner orbital complex
{•,{•·H),ClJSO, .. Ag' No reaction w ereas [Ni(NH 1 ),Jl< is an outer orbital
( 'it~H~;su,]CI AgCli. 1 (white ppt.) complex.
jl ,)(, 0ml In the presence of N H,. the 3d C'lectrons
· . n tile basis of valence bond theory
1 pa ir up leav ing two d o rbitals e mpty to be
£>P1a r\~N).l2" ion with square planar structure mvo. lvcd 1·n ' 12,,p1 h y b n'd 1' sa ho
. n furmmg
. mne
.
S· 1i,at ~N~agnetic and .the [NiCIJ 2• ion with r
3 orbital compkx in c.ise of [Co(NH 1 ) 1,]3+.
is dt dral geometry 1s paramagnetic.
In Ni( NH3)/+, Ni is in +2 oxida tion sta te
1e1ral1e jN i(CN)4}' Ni(28) : 4s 23d"
1 ~nd has d' configuration, the hybridisation
- Ni . (28) : 4s 3d~ 0
mvolved is sp3d1 forming outer orbita l
stron•• field ligand so, it causes complex.
·- 1G a o
CN. · of elect rons.
3,ring , 4, 4p ~~futhe number of unpaired electrons ·,n

. . E]L.lt WJJ
. p 1 hr briJ isation
J
th e square planer (Pt(CN) )2· ion.
mD For squ are planer shape,
4
the
square plJner hybridisation is dsp1. Hence, the unpaired
electro ns in Sd orbita l pair up to make one
. d':nnagnetic due to absence of unpaired
!I JS I, d-orbi_tal empty for dsp 2 hybridisation. Thu s
I ·trons. th e re 15 no unpaired electron.
,,,.,NiCI, f , Cl is a weak fie ld ligand so. it 1Pt(CN )4 j2-:
In I ot cause pairing of electrons
Pt(78): 6s'Sd9, Pt1• : 6susds
dot'" n 3,t ...4.' ................•1'
Srl 6s hp

[]I1[[IIlJ :rn~. ..1.t.m. m_TI! ::.;, ' hybnd1s...1 tion

IP•(CN)
4
J'· a!Ii !Ii m!fJJ[.1trL.JUlU1
rlsp 1 hybridisation
Tctrc1hcdr,1I gl'Ornt•t ry

. paramagnetic due to presence of unpaired

10. The hexaaquomanganese(II) ion contain s fi ve
!!JS unpaired electrons, while the hexacyano ion
electrons. contains only one unpaired electron. Explain
[NiCl,J2' is paramagnetic while !Ni(CO),J is using Crystal Field Theory.
6, diamagnetic though both are tetrahedral. mD Mn(ll ) has 3d 5 electronic con.figura tion.
Wate r is a wea k field ligand and thercfm e 6 ,
wt,y? N ... 11
ll! In Ni(CO\ _11s m zero oxidation state 1s sm all. Therefore, the hexaaqua complex
whereas in N1Cl. ·, it is m +2 ox1dahon state. will be high spin complex containing 5
In the presence of CO ligand, the unpaired un paired electrons. On the o the r han d, CN- is
d-<'lectrons of Ni pair up but Cl being a a st rong fie ld ligand and therefore, Ci,, is la rge .
weak ligand is unable to pair up the unpaired The refore, in its cyano complex, the electro ns
electrons. pa ir up and have onl y one unpaired electron .
COO) CD
1, [fe!HiOll+is strongly paramagnetic whereas
[fe(CN)6]3· is weakly paramagnetic. Explain.
mi:I In presence of CN·, (a strong liga nd),
the 3d electrons pair up leavi ng only one
i
...\,, !-m~1ll
i
.\ lari;e

unpaired electron. The hy bridisatio n is

J,p3 formin g inner orbita l com plex. ln the
CIX.tXf) l
Hi,;h <pin !Mn(l l,0)0 J"
®$XE) l
Lnw spin IMn(C,i,. j'·
 ~
~1,·i··f~
- /1/(;t'~I
1

·.
.-t,>l'I' ' .,, th< -.1,,.,.
lii: ,m.t• ,.,·,u,,, ,ldJ,1<\•nt
, , ,., ti.-n, It tho.· ,,,rn, I' ,,t ,u, 1><·t.1h,•Jr,11 nl d111t•rn11 !l1,1u,
hb1~ '~
l.t,\' .,.,. h.l,,
th. t~, 1.11 1•.,, l •..._,nwr \\ lwn l\n ,·, ,11111)!,, 11 11,, I)
11'v l'"''t,,,n, ·"'' .11\'un,I tlw ni.·ndl.ln 111 I{.r\t .N),, I 'I\ 1\ 1\ I Ji i11,, l,11
I''" t·nt It
11 1
th, ,x·t.1h,"1r,>t1 '" 1!1't th,• n1,•nd 1<1n,il \l111'r) buund 111 l , ,. '~ 11, ' 1... 1
I <lt\<J \• \ '
l'"'"ll"l't. 1h t'<~>rdin~t th,, l • · 11 lo
ll \.II 11)1) I', ., I I
lilt' NII I ' 0111,,,, '~-l 'I
'-.. l'I / \°N , '~"""' ,1r,, \ '(~1'••1 ,'
h1s,111d, t,,t,·.,,. l,,,1,1\ I 1J,J ,
ll
l~
" , u, M lonisa lion ,
isoni.•n s1 11 ' r· iso,l\~ris
. " is,,~ Wh in
t,, l fr,
, .
,,
<'om pit•, s,,lt • . en 11, , : t1 :
. I~ ll s,•jf I \ 1,,
',ln d ispl<1r,• ; 1· '1 Pl11 ll\,~I 1\
tl < l).\,ll1d ~t\t' <•1 "
w ~ount,•r 1011 /\ \vh,r1 1'11 1· 1•
' I\
I
t ,e ion,~.11ton is ''\,1rn111 ,, ti,_""'
I f ,i '• '
,
IC11(N I l,),BrJSO orners IC11u~/ t
1 P,
\\n ,

1
11).,,'''<t. .
(vi) Solvate · . •·
. 1s0 111 er' ~,. ,
rsnnwrism is k 1s111 . 111,
no,vn · 11.
111 r,1~,, wh,•r , a, 'h"d "•1
, ., . . . . \\l,ltt•r is . ' '•I I,~
11s 1ssi n,ilar t . · 111 v 1 ~,. ,.
. "ton is.it· 0 v~d ••~
Th, 1 1
-"- .11 \'~• I '""t
11wr1J11m.1l (me,) isonwrs differ l1 . ion I~•- •1 i,
' •'ll'Wr-,,1 (l Co(\l 11),( N0 ),1 rn,,lecul,, ·is ct · Y Wh Clhcr""1\1 tt,1, , · ",
i-
1 . irt'('tl b \)r ·>1 \ •,
hi) Optiul iMimerism : Uplt, ,11 ,~omerbrn i~ ,,r 111,•rdy prt•~nt y ondcct 1, not ,, ~-..
tlw crystal lattice ,Aas fr~., so1,c: th~'l ,> .
,,,mm,,n m '" l,ih,•dr,11 ('omplt•:>.,·s involving th . n exn ·•t 'n 1,,
t>,J,•nt.,t,• h)l,an,! , In •1 ~01Jrdin,1tion ,•ntity of . l' aqua co111plt>x IC ll\pic •1 <,1,l .',
th,. its solvatt• isnn1er [C .r(H20), lc1 Pto,,~"
• lPtC!.(r·•r),f" ,,ntv tlw cr,• isonwr shows
,,ph,al .tt t1 , 11\ . green). r\H20\c:1 1 l1·11i1 •,i
1<..1r1 1 111

Cl 7 2• Cl Cl
--Ii
·--,.. How many geolllet . .
h ncal iso
)\) 1 '
ir,
,
I Cl ......__ I _..,.,......._
t e following coord' . lllers ijr
.
(11 [Cr(C 2O,),]'- tnati 011 e llQ
1'11,,.--...,__Pt /

'-' C)
.. entities) ss;,,
Pl r,r
- . (ll)[C
(''-..J
('/Jj " ) T (1) Zero
(11
O(Nft,l,CI J
"'I ,

wo - Facia l and . '

dt:'\lr> m,ror
NH1 11lendiona1
IJ.t.'VO

('pt,-,! '"""'" (d dnd I) of n<-[PICl1(,·n),J''

c i.. . . .__ I; NH1 N11
1
NI-Ji
(iii) linkage isomerism : Linkage isomerism -
Co
,,
'\. I
c----
Ci
anx><, ma coordination comp0tu1d containing CI Cl NH:, Ci....- 1' \
amb1dentate ligand . A simpl<' exa mpl e fnc- NIJ \ Ci
1~ provided by complexes containing the 111er.
thiocyanate ligand, NCS , wh ich may bind -\().Draw the structu res of opt' .
• 1ea1,
through !ht' nit ro15en tog ivi? M-NCSor throu gh 3
(1) [Cr(C 1O,) 1] · (ii) [P 10111 ers 0r:
su lphur to give M-SCN . This bch,1viour was (iii) [Cr(NH 3) 1Cl 2(en)I' tC1,(en1,p,
seen in the co mplex JCo(N H3)s(NO2)JCI,., mJll (i )
which is obtain,:,d as the red form, in which r•·i
the nitrite ligand is bound through oxygen n ,i:
(-ONO), and as the yell ow form, in which /)(_)·<
the nitrite ligand is bound throu gh ni trogen
(-NO 2).
(iv) Coordination isomerism : 'This type
of isomerism arises from the interchange of
ligan ds between ca tionic and anionic entitic~
 159

12 •Write all the geometrlc.,1 i~omers of

[Pt(NH ,)(Br)(Cl)(py)) and how many of thciC
will exhibit optical Isomerism 7

- Nlf i__,__ B1 111 N...__ / l'y

l't / Pt
l'y
,...,... "-..
Cl ( I
/ '· flr
If N Cl
1-....._ /
!'I
/ ........
Br l'y
!\ II wi ll ~how optr c,d i, oml'ri~m.
13 • Aqueous copper sulphate solution (blue In
colour) gives :
(I) a green precipitate with aqueous
Cl 7+
potassium fluoride and
Cl I
" co/;.,, (ii) a bright green solution with aqueous
( '-J potassium chloride. Explain these
t'Hj laevo experimental results.
e!JII (i) Aqueous CuSO, solu tion .:ontnins
ICu(H ,O),]2' ions whk h impart blue colmir.
When KF is Jddcd, HiO being weak fi!.'id
ligand can be replaced by F form ing [CuF .1 2
ions which impart green co lou r.
fCu(H20Jd• ,- 4f - --> [CuF4 ]2 ,- '1H 2 0
[From KF(w/) 1 (Green ppt .)

(ii) When KC! is ;idded, Cl l igand rc p l,K<'~

2• I l,O form ing [CuCl, ]2 · iLJns wh ich h<1,.; bright
l't/1 7 g reen colour.
(____ ___,.Cl
Co f( u(Hi\))4'" + + 40 · fCuU 4 -+ 4i l~(l t
(j '--N 1t 1 {From Kc,..,,,) (Bright gr,.,,n solution /

rrnror
'"
oµtkal isonu_•n sm
ci~-isomcr 14. What is the coordination entity formed when
opti Gtl isotn~ri :,m excess of aqueous KCN is added to an aqueous
solution of copper sulphate? Why is it that
no precipitate of copper sulphide obtained
when H1S191is passed through this solution?
ma
tra n:- 1:--om ~r [Cu(H20)d+ ~K:s.:· -• {Cu(C:s.ll4] 2- .. -n,~o
lu~hl), -.t.,blt
CN i, ,trong fidd ligand, th.,rd uft',
;i

jCu (C!'.: )d' i, lti'\hfv <,t,1blt· .1nd ha, J.. ri,;c

q lu<' ,,f ,tab,ht, Clln.stant. On pi!~~mg H :S,
CuS i, not fomi,'d bt>caus.' this , oord111:rtion
entity doc~ not gr\'t..\ Ca~ i,,n.
 ~(Id,, '\,•~•~
160
"ktG- NCERT Soi
lllio

15.Discuss the nature of bonding in the following

c,.
coordination entities on the basis of valence "111
bond theory :
(i) [Fe(C N)6]•·
(iii) (Co(C 20 .)i]l-

8
Oil fFeF 6)3
(iv) (CoF )1·

(i) IFe(CN) 6 J•- : Fc(26) ha, ell'ctronic

6
Fn<•rgy
i /4 Au• rn~(' ,·nngy d
ti

I
,,
[~...;;-.;. lhl' ,I orb11 .,J.,, 111 a rv .,,... {
configur,1hon !Ari 4; l.1d". 11

-~.
/ bit ,I, splwn cal crystal \ pJ
1 1 or , fil'ld tll ing.,
F1: ' has electron1c c-onfiguration [Arj 4s23d" in fn 'l' ion t>c:tah..,J 1ct.,.lfii,
l-<irhitdl ')p\i1tmg
' in an octM\('d ra/ (ty ry~ J 1r
CN ion causc-s pairing of electrons becaus~ it ' ,1, 11,•ld 1• 1,.~
1~ ,1 strnn g hdJ li gand. As the ligand s approat h fi
. . , r~t th_
3./ 4s 4p increase 111 energy of cl-orbital \ ert i
. . re1• t I
Fc~· ITJit1lf(IJ_··_·_·_o _·.-..J·.-..··r .·.-.J.-.·..:·'IJ _ of the free wn Ju st a\ Would b.,. th.e1vt t,, I•:
sphencal held . c¾,, >"
[Fe(CN)"l
4
~ ""lur··1<).fJi_Ll!.] The orbital, lying along the axe~(d \
get repelled more strongly than <Hll(J rt
d2s113 hybridisation 11
It has octahedral shape anJ is diamagnetic in d_X'II I dI(..• and d:.r orbitals Which h 1

nature due to absence of electrons. di rected between the axes. av" 1,>t+
(ii) (FeF 6P- Fe(26) has electronic The d,2 and d,2 _ ,2 orbitals get raised
configuration [Ar] 4s23d6. Fe•· : (Ar] 4s''3d5 and dr; ti,,., d., orbitals are lower d •n~..
. e •n of
relative to the average energy in th ~ncr~
F bei.ng a weak field ligand, does not cause
pairi ng of electrons. crystal field . Thus, the degen " ~Ph~:,.'.
. . erate . ..,
3d 4s 4p . .... 4d d-orbitals get spht into t1Vo sets . 14:t ,
11 e1 .J'· rn rIr lUii _[Qt.1r~rJruJ_]] energy orbitals set, l2, and the high~, · tht Io.,,,,1·
,,r'J1 hybnd1-.Jhon, O('tJhed ro1l ~.i pe orbitals set, e,. The energy is '>€pa erx1~,
. , ' •l~d b1 I
(iii) [Co(C 20,)3]3- : Co(27) 17 •What is spectrochemical series>· EXpJ •
has electronic
configura tion IAr I -4, 2:lif.
difference between a weak field lig a,n t""
Co'· : IAr]4s03d" strong field ligand. al\d at\<i ,
C,O/- being a strong field ligand causes
g The crystal field splitting, .\ , ct,. ,
pairing of electrons.
upon the fie ld produced bv tht lio ~'
'
4, ........ .~/'. . . ___
lio,.,Jr1d ", "
mm thlflf ITJL "IT:l!D.If]j
. 3d
charge on the metal ion. Sornt
[Co(C204)3J3-li ,,and, i
able to produce strong field s in " h • ''
;~p'J hr b~1disation, 01.'tJheJ r,l l .-,hape l(, "-,
splitting will be large wherea, uth~rs pr,,,. ·"
(iv) [CoF 6]l- Co(27) has electronic weak field s and consequtntly rt'su!t ii· ~,, '.
configuration [Ar] 4s 23d7• .
splitting ot d-orb1tals. In ~--n~tJI, i:q~•
' ,.. ,.,,
Co 3 ' : [ Ar ]4s03d0 . can be arranged in d ,eries in th, vr,te, '
F being a wea k field ligand, cannot cause increasing field strength as g1\'en b<?lo,,
pairing of electrons. 1- < Br < SCN < ct-< 5:- · r .- Of·h L( .
1
!CoF,1 · !T T ll Ii Ii Ii] :~: [f]D[Gi a:i'.w
~;, lJ:! h,·bnJis.il ion, ._, -1.1ht'd.ral ~hare
H:O < NCS- <t'dt.1+·< \i l '-ill<('\-< -, :
Such a serie~ i,; lt>rmed a, >)'-!dr.,C:•,t,':";_:'
seriE's.
16.0raw figure to show the splitting of d-orbitals If .\, , I' th,· fourth c'.,·ctron ~m,·,, ,·.
in an octahedral crystal field, the t'~ l,rt, 1t.1 l~ ~1 \ ii,~ ~ht~ l.°\'nii;:.;.r Jh, - •~
m!I Let us ,1, sunw that the si x ligand, :'r(' LigJnd, 1,ir "hich l. •. f' Jr, ~n,•1,r, ,, -~,
posi t1011l'd , vmmet rica lly ,1 lun~ t_h" Cartcs1,in fi~ld ligand, ,md 1,>nn bgh ,;,,n ,, 'r?\•,
,i xc~, with m('ta l all1m d i the ongm. li \ -.. [' 1t l~-c•· nh."::- r.:,,,::\' ~r.( ~..: ..·t.: -
1
 161
21. ll'•(C1111 1•
nd
C-ol o o u •1 a ll'e( l-f,O>.l'• are o f d iffere nt
..,_ ndilut I
-..q 1 • so u tlon,. Why?
I 1. n 11'.•(('N ) I'
8 ••n,I h,, 11 " , I. N " ,, ~, rnni,: ft ,,Jd

L!-!.ll.] i n~- . . ,
Jt7l. l.\~, p.:11r1nn t I
n O t' e, tri.,n~ t ,1k, ·~ p lru ,.

ln (l· (•(l1
· n g d<
2 ls! , H l O J 'i.
.. lt.11 m_w J!
P atri .• .i w,• ..1 ~ li~.tnd h,•n <.". 1~,
ff Tr,,~ . )< s not tnl..c• plau•

8,,th J
1ru I!] ~
rm+~ l r, / · .l
. 11L. -·
I l
igan d s s l
Cl"yst al held ~ l (~·w diffr\ren t n1agn 1tudt.• ,)f
n ah irp
I P li t11 n g <'11(' rgy d u<' to d iffe re nt
a n s s h ,en ce, absorb differe nt wrtv,. . fc n g lhs
.. o w d ifferent co lo u rs
22 · ..
• D1Scuss the
carbonyJs nature of bonding in metal
@ab .

~ ~ c - o~
Syn e r-gic bond in g
The
tn e ta l-ca rbo n b o nd in m e tal ca rbonyls
p ossess b o th C
b . s a nd p ch a ra c ter. The M · a
nd
, agne ti c du e to presen ce o f unpaire d o IS fo rm e d b y th e donatio n of lo n e pair
of e lect .
3r,1 fl ro n s on the ca rbon y l ca rbo n into a
111~f'~r1!- v aca nt o rbita l of the m e tal. The M -C 7t bond is
<"l..ff
· ''-<cr-n,1-_;-"'
'! r •
forme d by the d o n a tion o f a p a ir o f e le ctro ns
Ni 2• ' 4 so3rl"
1"'10).-4,:-.:><• '
3d
4s
····························
4
f'.
from a fill e d d-orbita l of meta l into the v acant
a ntibo nding n* o rbital of carbon monoxide .
~w [1] [Hffil J
;- ~ - - - · · · ························· The metal to ligand b o nding creates a s ynergic
crJ)4J d s p 2 h y bridisa tion effe ct which stre ngthe n s the b o nd b e tween
,, 1\
CO and the m e tal.
I· pla nar s h a p e a nd is diam a gne tic

ft
ll'' 5'labLlsen
10
ar e
ce of unpa ire d e lectrons. 23 -Give the oxidation state, d-orbital occupation
and coordination number of the central metal
Joe 2
f [Ni(H 2 0)J • is green but a solution
ion in the following complexes :
~5olll
tionO
,- is colourless. Exp Iam. .
(i) K,(Co(C 2 O 4 ),J (ii) cis-[Cr(enl,Cl,JCI
.JI, .i·(Cllll• 1 . d I
1• /["' .( .... 0 ) 6 ]2• h as unpa1re e e ctronsdue (iii) (NH 4 l,[CoF4 ] (iv) [Mn(H 2 0) 6 JSO•
o [N' 1• 2
H O liga nds whic h abs orb light from
2
l:'mllll (i) K 3 [Co(C 20 4 h] - 0.5. = + 3, C.N. = 6,
,,eal< ·on and r a diate c o mple m e ntary 6
t0 . reg1 . 3d configuration = t ~Ke~.
_,j,,i,te . g r een where a s [N1(CN) 4 ] 2· does (ii) cis-[Cr(enl,Ci 2 ]CI - 0.5. = + 3, C.N. = 6,
, 0100<
v e an)
,.e., , unpaired e le ctro n due to strong d 3 co nfiguration= tt
~at }la and, the r e fore, does not absorb light (iii) (NH 4 ),[CoF 4 ] - 0.5. = + 2, C.N. = 4,
crJ· hg ·bl reg ion h e n ce, it is colo urle ss. d 7 configuration= t~ge:
..., v1s1 e
itD""
 W1.i70' NCERT S01u110 1J
! IC1
162
. ) Cs[h -C14JC 1esiu111tNrac·hlor·.,
(IV , l\l l)ft,
~,,J
0
(iv) !Mn{H:l)l,.\SI.\ O.S.• ' 2, C. N • ' Ox1d,1tinn st,11!' • +J rrutt' (I
11)
d' ,·onhgu ratmn • l~l: · No. • 4
coordin,1t1on
24.Wrlte down the IUPAC name for each of
Configuration ,. ti, r;
d' te the
the following compltxes aod in ica . Fe (26) : 4, 231•
oxidation state electronic configuration Fe ,, : 4sOJtl'
, ·ve 3d 4,
and coordination number. Also 9 ' ,........... 4p
.
stereochemistry ind magnetlC mom ent of the
[IT I t I_t I fl _lIT.11...:~
complex : W' hyhnd1sat101, fl'trahcdral ~ha Pe ·....1
,
(I) K[Cr(H2O)1(C2OJ 2].3H 2O ptiramagnl't k in nature '

(ii) (Co(NH 3),Cl]Cl 1 (iii) CrCli(pyh It is paramagnetic due to PreS(>

(iv) Cs(FeCIJ (v) K.(Mn(CN)J
unpairl'd electrons. l'icr 01 ,
Bml (i) 1<!Cr(Hi0)z(Ci0,h ).3HP )

Pot1ssiumdiaqu.ad1oxak1tochromate 011) hydrate µ = fn(n+2) =M = -Es =s.92 B.t,,i

Ox1dJtion ~tale • +3 (v) K4[Mn(CN).] Potassium ·
C.N • 6,
hexacyanom
configuration • rt angan
3d 4, •r Oxidation state= +2 ate(lf·

It Ii It 1··wll -tnl . ff iif¥]i

.
Coord ination no. = 6 )

Configuration = l2g'
A,,-3 hybnd1~ t10n, ......~; w;a, ·..h~·; .~--~ r~n~"'~~tH'm n.1ture
Mn(25) : [Ar) 4s23d5
µ = J n(n + 2) = &s = = 3.87 B.M. Mnl• : [Ar I 4s03d5
(ii) fCo(Nl-! 3),010 2 3<1 .....................4.:.. 4p
Pentaammine<"hloridocobalt(III ) chloride
Co(27) : 4s23,f
CT m!I t IHlrJl. ...lDL.·:.[fil]I]1
J 'si1-' hybnd1sation, octahed ral sha ........ ,
Col-: 4s'>Jd6 paramagneti c in nature pe,

Ii !Ii i11 i[· W~l ff] 1rmW~I: µ =Jn(n+2) =M =1.7328.M

d1.sp3 h yb n d isat10~ ~ aht.--ct ral, ·d1~~aSfletic in n;~ re
The oxida tion state of Co= +3 2S,Explain the violet colour of th
3 e corn
C. N. = 6 [Ti(H 2O)J • on the basis of crystal fi Ple1
I
Configuration = t~ a . . edtheo
Electronic configuration of ii" . 1).
µ = O B.M. 3d 1• Due to the presence of ligands _IS IA.rJ
(iii) [CrC1 3(pyh] d-orbitals are split into two sets f' Its five
0 Orb·
Trichloridotripyridinechromium (JII) three with lower energy and oth llaJs
er two .
Coordination No. of Cr = 6 higher energy. So, there occurs d-d tr . With
Oxidation state= +3 <1!1s1ij
between these two sets of orbitals ln ons
Configuration = fix . gro
state, the only d-electron is present . llnd
Cr(24): 4s 1 3d5
in any
of the three d-orbitals with lower en one
Cr>' : 4s°3d3 . . ergy.i\ft
absorbmg light energy in the visibl . er
3d 4s 4p . e~~on~
the spectra, this d- electron is promoted lo
It Ii It I: m~1.. fQ....l nltWJl1
d2sp3 hybridisation, octahedral shape,
other set of d- orbitals with higher ener the
. b b . d gy, As
1t a sor s m green an yellow regio
paramagnetic in nature .. m o1the
111s1ble spectra the transmitted light 1-5 d
re and
µ = J n(n +2) 3.87 B.M . violet i.e., purple.
 rl,, ,
,,l I .u 163
·, ' ,: ,,rit by the che ott t1rtct? Give an
1s JII
,1 of formation of coordination entities, form
I' pie· di-or polydentateb'ligand uses
.It, , 111 '11(•11 .1
the b1s1·s I h · . · ·
' · or t e1r detection and est11nat1011
,' ~I 1\ · • donor at0ms to md
111 ort
a single by classical and instrumental methods of
. , ,,r it I~~'
f\\ l
.. iid 10.be a chelate. ligand . The. analysis. Examplt•s of such reagmts incl ude
,r •,,\1 ,,,n.( ,.Ill·h ligating groups 1s call<'d the
11 O
h EDTA, DMG (dimethylglyoxime), a-ni troso·
1, · 1 , ligand. Sue complexes, called
i,..•r ll-naphthol, cupron, rte.
1 ,~1 oft" • ,.,.
11,.,,1,,11)' ,1t1!,\exestend to "'-'..more stable than
(iv) Some important extraction processes of
,,, 1,t~ ,~ Je~~s contammg unidentate
metals, like those of silver and gold, make
,,i,,·11i.,r c0rnPple : EDTA, DMG, etc.
.,0 , Exarn use of complex formation. Gold, for example,
1nJ · · 1 •
rf • giving an examp e 1n each Cise combines wi th cyanide in the presence of
brtt11 y . d.
. ,~ss rdinat1on compoun 1n : oxygen and water to form the coordination
()JS ofCOO
if' 11' role .,al systems en tity IAu(CN)i J- in aqueous solution. Gold
t bio 109_' 1chemistry can be separated in metallic form from this
1·1 ·,,ria
1
'. .1 111ed ·cal chemistry solution by the addition of zinc.
I''..) 3nalyt' . /metallurgy of metals.
(ii' action . 28, How many ions are produced from the complex
(1•
. I ,,tr(') C(J<Jrdinahon' compounds .
are of
Co(NH,)6Cl1in solution?
1
J<Jrtance in b1ologiral systems. The (a) 6 (b) 4
1 1111
,•f\•' 1 1 re snonsible r tor photosynthesis, (c) 3 (dJ 2
' •0,~nt •s J coordination compound of
f''F 1 11111 1' I h lml (c) : 3 ions are produced by [Co(NH3),!02-
.~1,,r, P_• 1 Haemoglobin, t e red pigment
51
'rt\•,cn~
C d'in\\'··hI·ch acts as oxygen carrier is a [ Co(N H3)6 ]Cl2 --+ [Co(NH3)6 )2+ +2ff
,,' 1 1,ioO .
.111 auon compound of iron. . Vitamin
29,Amongst the following ions which one has the
,,,,rd anocobalamine, the. anh- . pernicious highest magnetic moment value?
S,:· c~ · foctor, is a coordmahon compound
11 (a) [Cr(H 20)6]3• (b) [Fe(H 0),J2'
J11,11,n a Among the other compounds of 2
(c) [Zn(H 20) ]2•
i " ,bail-. 1 portance with coordinated metal 6
'' ··al in
t,i,,to&'', the enzvmes like, carboxypeptidase - (b) : Cr3' - 3d3, Fe2· - 3d6, Zn 2' - 3d 10
0n; arc bonic anhydrase (catalysts of Since Fe2' has 4 unpaired electrons, it has
1 and car
.~ . al svstems). highest magnetic moment.
t,iologtC · '. growing Interest in the use of
1n~re ,s d. . l h . A 30,Amongst the following, the most stable
(iil , therapy in me ICma c em1stry. n complex is
31
(hd ' , . the treatment of problems caused
,pie IS al . . . (a) [fe(H20)6]3• (bl [Fe(NH,JJ''
,,.in presence of met s m toxic proportmns
(c) [Fe(C20 4),]'· (d) [FeCIJ'·
t,1· tJie ti •mal systems. Thus, excess of
. Ian ant . - (c) : Since C20,2" is a bidentate !iga nd ,
in P d iron are removed by the chelatmg
copper a;_penici!lamine and desferrioxime B it forms the most stable complex.
!igaotls ation of coordination compounds. 31, What will be the correct order for the
,,iat]ie /orr:sed
15 in the treatment of lead wavelengths of absorption in the visible region
EDTA . Some coordination compounds for the following :
paisoning. effectively inhibit the growth of
. plattnum . 1 . d 1 d [Ni(N0 2)6J•·, [Ni(NH,)J 2', [Ni(H,O)J''7
tumours. Exa mples are: c1s-p ahn an re ate
ot
- In spectrochemical series the order of

com Po unds. the given ligands is H20 < NH 3 <No,·. Hence,

"')1 co0r d'ma tion compounds find use in
(11 ualitative and quantitative chemical
manYs_q The familiar colour reactions given
analy is. . 5 with a number of ligands
b meta 1 ,on
Y . 11 ), chelating ligands), as a result
(especia
the wave length of light will be absorbed 111
. he
the opposite order smce E= T ·
Hence, the order of absorption oi light will be
[Ni(N02).!'1• < [Ni(NH,)6!,. < [Ni(H20 ),l2'·
 ~-t;G- NCERT Solut·
ions (C
166 la~

19, Which of the following colll ''J

Rl.'arran)l;rmcnl \ 1l \ 1l \ 1l \~
homoleptic? Pie~,,
(a) [Co(NH3)6]3• (b) [Co(Nfi
,12 11,3 h)'bridis.1tion
(cl [Ni(CN),]2- (d) [Ni(Nfi 3l• Cli]>
(a, cl : In complexes ICo(N l4c1,l
3
No unp-ii red electron hence, diamagnetic. -

(c) [Fe(CN)6)+- ; Fc2': 3'f' filililllil [Ni(CN) 4f-, both Co and N·1 li,)bP',
·
to one kind of ligands onl y he" e ~ttilc
ar
homoleptic. ce, th~Y ~~tj
Rearrangement
•r~
20,Which of the following
heteroleptic? cornPle~es
1l's1•' hybrid1~a1ion (a) [Cr(NH3)6]3+ (b) [Fe(Nfi
(cl (Mn(CN)6J 4- (d) [Co(Ni•Cl,J,
No unpaired electron hence, diamagnetic.
mD (b, d) : In complexes' IFe(N3l4C1,J
.
16.Atomic number of Mn, Fe, Co and Ni are 25, 26 and [Co(N H3)4Cl2l, metal is bo d li3)1c:1
1
27 and 28 respectively. Which of the following than one kind of ligands h n ed lo "'1 1',
. ence th ·· or
outer orbital octahedral complexes have same
number of unpaired electrons?
heterolepllc. ' ey
•r~
(al [MnCl 6]3- (bl [Fef 6] 3- 21,ldentify the optically active comPo
11
3
(cl [Cof 6J - (dl [Ni!NH3lJ2+ the following : 1\ds fr 0
(al [Co(enh] •3 (b) trans- [C 1li
Bml (a,cl:
(c) cis- [Co(enh C1 2]• (d) [Cr(Nli l o(enliCI )•

~J-~ ]
[MnC~]>- : Mn 3' (3d4) \ t \t \ t \t \ ] _. l . [C ( :i.
mlllll (a, c . o enh]- and cis[C
3 sCIJ l

! ["'-~
r
~ '.:l
[CoF6]3- : Co '3
(3d6) I1l \ t \t \t \f] 3
17.Which of the following options are correct for
[Fe(CN)J 3- complex? 1 +
/ Co / en en / '-. ;>/
(a) d2sp3hybridisation (bl sp3c/2 hybridisation
t]··~_/ \
i 1

(cl Paramagnetic (dl Diamagnetic [ ~t) / : '

Bml (a, cl : [Fe(CN)6]>- , I

l1l I1l It I : I : I [] -1:\-:\-:l Mirror

C~ Cl
d'sp' Hybridisation
Magnetic nature - paramagnetic.
"I 1·
18.An aqueous pink solution of cobalt(II) chloride
(jco(J 11

en
changes to deep blue on addition of excess of
HCI. This is because_ _ _ _.
22. Identify the correct statements f
(a) [Co(H 20)J 2• is transformed into [CoCl6]4-
(b) [Co(H 20) 6]2+is transformed into [CoCIJ 2- behaviour of ethane-1, 2-diamine as
19
at a
the
(a) It is a neutral ligand. lld.
(c) tetrahedral complexes have smaller crystal
field splitting than octahedral complexes (bl It is a didentate ligand.
(d) tetrahedral complexes have larger crystal (cl It is a chelating ligand.
field splitting than octahedral complex (dl It is a unidentate ligand.
mll (b, c) : Pink solution of cobalt (II) e!m'I (a, b, c) : Ethane 1,2-diamine is ar«'lltta
chloride changes to deep blue on adding and didentate ligand . It is a chelating .igern.
excess of HCI. [Co(H 2O) 6f· is converted to NH2- CHp-12- NH1
[CoCl 4 )2- and the tetrahedral entity have NH2-CH 2
smaller crystal field splitting than octahedral
complexes.
-M
< NH1 -CH~
l
I .

'JTtlp<J()lldS
f!O'' L. 167
°"'
,~/119 I
following comp exes show linkage
. hofthe 28.on the basi 5 0 f
~,,.. 1 why C crystal field theory explain
0(111) fo rms paramagnetic . octahedral
:J·.o111erisJ11H1J1(N02JJ1' (bl [Co(H20lsCOJ3•
complex with weak field ligands whereas It
~) [Co(N.., ) scNJ2' (d) [Fe(en)i Cl 2J• forms diama
fJl rcr(NnJ) .I N l )· ,incJ SCN ,Ire ,1mbidcntnt-e .
t gnetic octahedral complex with
I''.:.d.11 (a, c ·,, ,ht'"'
• hnl,..,1g,
. 0 .
1~unwris111.
s rong field ligands.
!,'I""" j, 1i,•nc-- · lml w·ith weak li.,a nds A < P 11w
\l~Jtl\. · eIcctro · , . 0 ....,, ·
,2 ntc configurdtiun of Co( lll) will be
Short Answer Type Questions 14
li!' x wi th 4 unpa ired electrons and it is
paramagnetir · w·rth strong field lh,a nds l\, > P
~ e the following _c~mplexe_s in the I1cncc the .,1 . o
. ' c ectrornc configuration of Co( III)
,rra119 rder of conduct1v1ty of their solution .
1,r sio9o
if'crt3 ) Cl 1 [Co(NH 3),C1 1]CI, [Co(NH 3) 'Cl
. will z~ ,
. be 11, e'° wit· h no unpaired tdectron a nd is
t:I 1amagnetic. '
' t,lHi J l ' 6J ],
1col l cnc12 29.Why are low spin
· tetrahedral complexes not
~Hi~o(NH ,l,Cl,d < [Cr(NH,l,Cl 2 )CI <
formed?
~ - ' .),Cl]CI: < [C,)(N H,)..!CI.,
. . .·it,· ,kpem:I s on tic
[l.•,(i' h.. l
number of 0!ml Low spin tetrahedral complexes arc
•111c1,1,t1 1 , . not !omwd because
. • tetrahedral complexes
for
l, . , ·t'd in the solu llon. Ln the order
lflJUl1l the. CFSE
. is Iower than pamng
. . energy hence,
"111' f pleices produce 1, 2, 3 and -I ions
tJie com pamng of electrons does not take place.
,,.,(liWlv.
tf:'t" . 30.Give the electron1e . configuration of the
o0rdination compound CrC1 3·4H 2O
following com PIexes on the basis . of crystal
iSJ i~itates silver chloride when treated with field splitting theory.
pteC itl'ilte, The molar conductance of its [Cof.Jl ·, [Fe(CN)J•- and [Cu(NH3)J2+.
·I~r n
• corresponds to a total of two ions
11
soiutiOtructural formula of the compound and
0!ml [CoF6].1- : Co:i. (116)
wn1es
r,arneit. . . .
'1'Jlll It gives white . prectp1tat~ of AgCl
. h !>.gNO3 it means 1t has Cl· 10n outside t\e/ 1l t t t t
\\l{t I • • •
e eoordinat1on sphere. Smee 1t gives
: nductance of two ions the formul a will be
1co(HP)P2JCL Its IUPAC ~ame is [Fe(CN)0 ) '- : Fe2' (d6)
tetraaquadichlondocobalt (III) chloride.
26,A ,omplex of the type [M(AA)iX2]"+ is known
to be optically active. What does this indicate
1,oUt the structure of the complex? Give one
1
example of such complex.
di An optically active [M(AA}iX2).,. indicates
,;;,octahedral structure t\1/· cis-[Pt(en)i02]'" or
,'6-jCJtenJz0 2r 16, e8J , - - , --,-- , . - - , ~
-I 1l 1l 1l 1l t
27,Magnetk moment of [MnCIJ 2 - is 5.92 BM. 1l 1l 1l
Explain giving reason.
BIii 5.92 BM corresponds to 5 unpaired 31.Explain why [Fe(H 20)J 3+ has magnetic moment
tlectrons in d-orbital of Mn 2 ' ion. The value of 5.92 BM whereas [Fe(CN)Jl- has a value
ofon ly 1.74 BM.
hybridisation wili be sp3 and structure is
' tetrahedral. mml {Fe(CN) 0 ]3-· :
LJ
'\\nCI.J'- 1r- t..,-
t ..--! 11'-,- 1' j
1t-,.1~
-----
1<pt
j : I: I:
hybndisallon
j 11~I1t It I : I : i l : I: I : I
l68 M.tG- NCERT Sotu/'

-...
_ . Matching Typ, Q"'s
ions <c,
~,)
Nate: /,1 t/1,·Jolfowi1151 questions lllntc/1 '
· 1hr ·
111 Columns 111111/ 11. 11r,~s Ri

Due to prt>sence of j unpaired electmns 36.Match the complex ions given in C

the colours given in Column II Olutrin
[Fe\H:O).P· has magnetic moment 5.92 B.M
correct code : and assign1 ,, . ,~L
whereas [h'(CN).f- has 1.74 B.M magnetic
Column I Colu \
moment due to prt>sence oi one unpaired
(Complex ion) (Coro"'" 11
electron. \l t Ur)
A. [Co(NH3}6l 1. Violet
3
B. [Ti(H 1O)J ' 2. Green
32.Arrange following complex ions in increasing 1
C. [Ni(H 10)J ' 3. Pale bl
order of crystal field splitting energy (~ :
D. [Ni(H1Ol. (en))1• (oqJ 4. Yeuo.. ,Ueh
[Cr{Cl)J l--, [Cr{CN)J 3· , [Cr(NH 3)6]3+. .. ,s 0
5. Blue range
R CFSE mcreas..>s in thl' order oi Code :
[Cr(Cl). J'· < Cr{NH,). J>- < [Cr\CN).J3"· (a) A (1) B (2) C (4)

depend ing upon the strength ,,1 the field . (b) A (4) B (3) C (2) D (S)
D(l)
(cl A(3) 8(2) C(4) D
33.Why do compounds having similar geometry (dl A(4l R(11 C(21 ol!!
have different tNgnetk moment? m111 (bl: (4), B (3), C --) ( )
2
' I) ..., (j
Bml It is due to the r resen~ of weak ,md
37.Match the coordination compounds . 1
strong ligands in cumple:>-es. U CFSE is high Column I with the central metal atoms9'~en in
the complex ,..-i ll show low value of ma.gnetic Column II and assign the correct COde _9,v~ in
moment and ,ire-,'t'rsa. e.g., [CoF0 ]>- is
paramagnetic with 3 unpaired electrons while
[Co(NH,l.t" is diamagmtic with O unpaired
Column I
(Coordination Compound) (Central
A. Chlorophyll
Colu ·

1 Rhn-'• afnin1
n:u
. . uu1um
electron. 8. Blood pigment 2. Cobalt
C. Wilkinson catalyst 3. Calcium
34.CuS04 .SH 2O is blue in colour while CuSO 4 is D. Vitamin B,2 4. Iron
colourless. Why? 5· Magnesium
Code:
Bml In CuS0.-SH20 , water acts as ligand
(a) A (5) B (4) C (1} D (2)
and causes crystal field splitting. Hence, d-d (b) A (3) B (4) C (5) D (1)
transition takes place and hydrated CuSO, (c) A (4) B (3) C (2) D (1)
shows colour. In anhydrous Cu504 there is (d) A (3) 8 (4) C(l ) D (2)
no ligand hence, crystal field splitting is not mil.I (a): (5), B (4), C -, (1), o __,
121
possible and it is colourless.
38.Match the complex ions given in Column IWitJ,
3S.Name the type of isomerism when ambidentate the hybridisation and number of unp.iired
electrons given in Column II and assign the
ligands are attached to central metal ion. Give correct code :
two examples of ambidentate ligands. Column I Column II
0alDI Ambidentate ligands have two different (Complex ion) (Hybridisation,
sites for attachment to the central atom hence, numberofu~
they show isomerism which is known as electrons)
A. [Cr(H1O)J '3
l. dsp1, 1
linkage isomerism. It arises due to different
8. [Co(CN)J1• 2. sp3cP,s
si tes of linkage e.g., [Co(NH 3},N0 2]Cl2
C. [Ni(NH 3)6] 2' 3. cl2sp 3, 3
and [Co(NH 3)s0NO]Cl2 or M r- SCN .md D. [MnF6J._ 4. Sp3, 4
M ~ NCS. s. Sp3ci2, 2
 If

169
oJ' ; B (1) C (51 D (2) Coct. :
' ,4 (3l 8 (3) C (21 D (1) (a} AO ) B (2) C (4) OfSJ
l~ ,A fA) 8 (2) ( (4) 0(1 ) fb) A (4 J 8 13) C (2) D Il l
,A 13) B(1 ) C (2) D (3) (c) A (S) 8 ( 1) C (4) 0 (2)

a~,._
,4 fAl . A __. t3), B -~ m, C (51, D (2) Id) A (4) B (1) C (2) D (3)
'.;.s (, ) -~
- (<.) : A -; (5), B _. (1), C ... (4), D -, f21
P""' HI ·

~ 9,.':l=l=I .\"ote · 1,1 iL- ·,,

1
ASHt'tJonftRN~T'1J)e
" " lh ,r.1•111:,: quc<tz..,,,, , t,.r,we11 / of
11svr!1,»i 1<,{l.:ni>ed i.. . ·
( L, ' ' ¥ ll , tatemenr ,,( r,·.1.-.m ,- \'11~·11
"<'\.';.> lite <WTe, I a11<wrr ,>ut , 1f 111.- 'i.•/1,,r,-m ~ ,-/;o,. ,·,:
r,u A:-'<..,.t,,,,1 an,f r t\J'(H, l~,rh uu ftt, f ~Ca">4m r:-
,·~,rr«•d < t pfo nah,trt oj assn-1,a,,.
//,J •~ i o n a11d ' l'IIS<m l'<Jtlt are t rnr but rMsm1 ,.,

lo
1101
.a.,.~ l /v rorrrc/ r:rplu11at ,,m ,,r· as~ rl 1011
...-~ " ""I " l ru<'. ro'a._<(t11 If fa!M
I di As,.-rt1011 N f.?/<,• rril5(i r, i, INJt .

4 l . Asser1ion :T~k metal Ions are re moved by th•

chebting ligands.
lt..$0ft : Chel<11te c.omph,xes t•nd to be more
stable.

the complex species gfven in Column 1

11'111 (a): When u solution of chelating ligand
'° ~tch
,,. .somensm
possible 1 . .
given . Col umn II
in
" added to solution containing toxi c metals
_.j!tltllr ligands che.lates the meta l ions by formation
inn the correct code : l'f s t.:ible complex.
,nd asS,:, (-•· ·-
ColUmn I unm,n II
(COIIIPlex species) (lsomertsm ) 42.Assertion : (Cr(H 20)JCl 2 and (Fe(H2 0)JCl 2 are
,._ iCo(NHJ),Cl,l' 1. Optical reducing in nature.
B. cls-[Co{tnlzCl,J ' 2. Ionisation Reason : Unpaired electrons are present in
C !Co(NH, l,(N0, )1O , 3. Coordination ttteir d-orbitals.
o: (CoiNHilJ[CI(CN)J 4. Geometrica l l:m (bl : In the complexes. Co exists as Co2•
s. Linkage and Fe as Fe 2•. Both of the comple xes becomes
codt: stable by oxidation of metal ion to Co '' and
ti ) A(l ) 8 (2) C(4) 0 ( 5) Fe'·.
lb) A(4} 8 (3) C (2) 0 (1)
(cl A(4l 8 (1) C (S) 0 (3) 43.Assertion : Linkage isomerism arises in
Id! A{4) 8 (1 ) C (2) 0 (3) COC>rdinatlon compounds containing
ambldentate ligand .
• {d) : A -, (4), B (1), C (2), D -. (3)
Reason : Ambldentate ligand has two different
IO.llitch the compounds given in Column t with donor atoms.
the oxidation state of cobalt present in it (given m!I (a) : Linkage isomeris m arises due to
ii Column 11) and assign the correct code. two d ifferen t donor ato ms in ambidenta te
Column I Column II ligand .
(Compound) (Oxidation state of Co)
A. !Co(NCS){NH 1 ),J{S03 ) 1. +4 44.Assertion: Complexes of MX6 and MX5L type (X
8. [Co(NH,),Cl 2JSO4 2. 0 and Lare unidentate) do not show geometrical
C. NaJ Co{S20 1).J 3. + 1 isomerism.
0. (Co2(CO).J 4. +2 Reason : Geometrical isomerism is not shown
5. +3 by complexes of coordination number 6.
170 ~G NCERT So/ulio
Ila (C1
a1,i
B (c) : For nimpl<' X<'S of MX 1, ,1nd MX1/. ( o l• • Jif" ' fr'

typl', Jiff1•n•nt );l'Onwtric ,1rr,ing,•nwnh 11( 1h,• Num lw r of unpai red cl1c< tro11s '" 'J
ligands is not p,)ssibt,,. Diarna8nel ic.
,\.1A 41l1, M(/\A)~/l1 and MA ,IJ, ty(->l' of <\ 1mpif>x1.-; (ii ) FeF. 1 :
arr th1• ct1mpl1' x,'s wi th crn1rdination nulllbl•r
6 which show i;cnnwtriral isonwri~m.
45.Asstrtlon : [Fe(CN) 6 Jl ion shows magnetic
moment corresponding to two unpaired
electrons.

Reason : Because it has c/2sp3 type

hybridisation. Nu mber of unpairi.'d CIC'clrons -
5
0lml (d) : !Fe (CN) 6]1· ion shows magneti c Magnetic moment " ._;5,/;: 2J : : 5.91 B~i
moment correspond ing to one unpaired [Fe(H 2Ol&l2· :
electron.

long Answer Type Questions ~ '•

46.Using crystal field theory, draw energy level
diagram, write electronic configuration of the
central metal atom/ion and determine the Fe2• = 3d6
illIIIEi.
magnetic moment value in the following : Number of unpaired electron5. 4
(i) [CoFJ 1· , [Co(H 20)J 2•, [Co(CN)J 1·
Map 1etic moment = ~ " t 9 B.~t
(ii) [FeFJ 1· , [Fe(H 2O)6 )2+, [Fe(CN)J 4·
[Fe(CNl6lt--:
Bml(i)
c~ e,

[CoF6J3- : 1l t t t t 1l 1l 1~

1l t t lzg
Co3• = 3d6 Fel· 3d"
C

Number of unpaired electrons = 4 Diamagnetic.

Magnetic moment
47.Using valence bond theory, explain 1!it
= + 2) = 2) =4.9 B.M.
following In relation to the complexesgiv!!i
(Co<H20l6J2•: below:
(Mn(CN)J 3· , [Co(NHJJ' •, (Cl{HiOJJ'" , [~ .._
(i) Type of hybridisation.
1~ 1~ t t t (ii) Inner or outer orbital complex.
1~ 1l t 12s (iii) Magnetic behaviour.
Co 2'=3a' (iv) Spin only magnetic moment vilue.
Nu mber of unpaired electrons= 3 ml1I fMn(CN)Jl-:
J:072j = 3.87 B.M ,
!1LI t l t I : !: 1 CJ j : l : ,:,
1J 4:- ¥
Magne ti .: moment ~
[Co(CN) 0 J'.I-: Mn'• =
('
g (i) HybridisJtion • ifs,r'
\it) lmwr ,)rbit..il , nmpl,•,
1L 1L 1~ (ni) l'~t,lllhl!!.l'll'hc
1L 1L 11. '.:.x i.;; 6 \:
(i\') M..i~J"lt'tic 1oom11nt w •t• - 1 · _,
~ - ' • ;: •; - V ,.
 171
cornpounds
,,1i0/l
.,, (i) Isomer A reacts with AgNO1 but not
with BaCli, it shows it has o - ion outside the
1c:_,, 3i l " ~ . .. . coordination sphere.
(,' ·Jisation -d1W Hence, A =[Co(NH3)s504]Cl
·'I Hybfl b'tal complex Isomer B reacts with BaCI 2 but not with
I' )rlller or ,
AgN03, it shows it has so/ - outside the
• 1oi . magnetic
iii) o,a etic moment = 0 coordination sphere.
. >vtagn Hence, B = [Co(NH3)sCl]S04
i:,J_ · ol~Jl+:
1crt~z _; t t t : :
D: I : I: I : I (ii) Ionisa tion isomerism
;, ,Jd (iii) A = Pentaammjnesulphatocobalt (III)
(r . .n p3
i ,bridisation - u-5 chloride and
1ii I ) orbital complex B = Pentamminechlorocobalt (UI)
·)1 lnJ1er
\i gnetic sulphate
1
) parama
1° , 1 gnetic moment= + 2) = 3.87 B.M.
(ti') J\'la 49.What is the relationship between observed
, lfetCU6JI-: colour of the complex and the wavelength of
light absorbed by the complex?
~[J[l=l=J l:1:1 I I I mmll When white light falls on the complex,
ri)
'
Hybridisation - sp
3tf2 some part of it is absorbed. Higher the crystal
_ Outer orbital comp1ex field splitting, lower will be the wavelength
~) . absorbed by the complex. The observed colour
") Paramagnetic
(lll of complex is the colour generated from the
(iv) Magnetic moment= 4 + 2) = 4.9 B.M. wavelength left over.

d,CoSO,CI.SNHi exists in two_ isomeric forms_'A'
and '8'. Isomer 'A' reacts wrth AgN0 3 to give
white precipitate, but does not react with
Ba(i . Isomer 'B' gives white precipitate with
1
Ba(i but does not react with AgN0 3• Answer
1
the following questions.
fi) ldentify'A' and 'B' and write their structural
formulas.
[Ii) Name the type of isomerism involved.
i) Give the IUPAC name of'A' and'B'.
lw
II CoSC\0-5NH3 :
SO.Why are different colours observed in
octahedral and tetrahedral complexes for the
same metal and same ligands?
B Lower wavelength is absorbed in
octahedral complex than tetrahedral complex
for the same metal and ligand. In tetrahedral
coordination entity, formation of the d-orbital
splitting is inverted and is smaller as com pared
to the octahe<lraJ field splitting. For the same
metal-ligand complexes, it can be shown that
~ , = (4/9)~0 -