IIT JEE Coordination Compound Etoos DPP

(1)

T Tooppiicc PPaaggeeNNoo.. T Thheeoorryy 0011--1122 E Exxeerrcciissee--11 1133--2244 E Exxeerrcciissee--22 2255--3322 E Exxeerrcciissee--33 3333--3388 E Exxeerrcciissee--44 3399--4400 A AnnsswweerrKKeeyy 4411--4499

Syllabus

Coordination compounds: nomenclature of mononuclear coordination compounds, colour Coordination compounds: nomenclature of mononuclear coordination compounds, colour (excluding the details of electronic transitions) and calculation of spin-only magnetic moment; (excluding the details of electronic transitions) and calculation of spin-only magnetic moment; cis-trans and ionisation

cis-trans and ionisation isomerisms, hybridiisomerisms, hybridization and geometries of mozation and geometries of mononucleanonuclear coordinatir coordinationon compounds (linear, tetrahedral, square planar and octahedral).

compounds (linear, tetrahedral, square planar and octahedral).

Name : _

Name : _________________

_____________________ Contact No. _

_ Contact No. _______

___________

_

ETOOS

INDIA.COM

India's No.1 Online Coaching for JEE Main & Advanced

3rd Floor, H.No.50 Rajeev Gandhi Nagar, Kota, Rajasthan 324005

HelpDesk : Tel. 092142 33303

Coordination Compound

IIT JEE 201

(2)

ETOOS

ETOOSINDIA.COMINDIA.COM

India's No.1 Online Coaching for JEE Main & Advanced

India's No.1 Online Coaching for JEE Main & Advanced 3rd Floor, H.No.50 Rajeev Gandhi Nagar, Kota, Rajasthan 324005 3rd Floor, H.No.50 Rajeev Gandhi Nagar, Kota, Rajasthan 324005

Page No. # 1 Page No. # 1

COORDINA

COORDINATION

TION COMPOUNDS

COMPOUNDS

Coordination Compounds :

Those addition compounds which retain their identityThose addition compounds which retain their identity (i.e. doesn

(i.e. doesn’’t lose their identity) in solution are called coordination compounds. For example, when KCNt lose their identity) in solution are called coordination compounds. For example, when KCN

solution is added to Fe(CN)

solution is added to Fe(CN)₂₂ solution, the species formed when dissolved in water no longer gives tests solution, the species formed when dissolved in water no longer gives tests of Fe

of Fe2+2+ and CN. and CN. Fe(CN)

Fe(CN)₂₂ + 4KCN + 4KCN ! ! !" !"_Fe(CN)_Fe(CN)

2

2 . 4KCN or K . 4KCN or K44 [Fe(CN) [Fe(CN)66] ] ((aaqq..)) 4K4K++ (aq.) + [Fe(CN) (aq.) + [Fe(CN)66]]44 – – (aq.) (aq.)

Various Terms Used in co ordination compounds :

Central Atom/Ion :

In a coordination entity

In a coordination entity – –the atom/ion to which are bound a fixed number of ligands in a definite geometricalthe atom/ion to which are bound a fixed number of ligands in a definite geometrical

arrangement around it, is called the central atom or ion. For example, the central atom/ion in the coordination arrangement around it, is called the central atom or ion. For example, the central atom/ion in the coordination entities

entities :: [NiCl[NiCl₂₂(OH(OH₂₂))₄₄], [CoCl(NH], [CoCl(NH₃₃))₅₅]]2+2+ and [Fe(CN) and [Fe(CN)₆₆]]33 – –_{are Ni}_{are Ni}2+2+_{, Co}_{, Co}3+3+_{and Fe}_{and Fe}3+3+_{, respectively}_{, respectively. These centr}_{. These central}_al

atoms

atoms / / ions are also referred to as Lewis acids.ions are also referred to as Lewis acids.

Ligands :

The neutral molecules, anions or cations which are directly linked with central metal atom or ion in the The neutral molecules, anions or cations which are directly linked with central metal atom or ion in the coordination entity are called ligands.

coordination entity are called ligands. These may be simple ions such as Br

These may be simple ions such as Br – –_{, small molecules such as H}_{, small molecules such as H}

2

2O or NHO or NH33, larger molecules such, larger molecules such as

as HH₂₂NCHNCH₂₂CHCH₂₂NHNH₂₂ or N(CH or N(CH₂₂CHCH₂₂NHNH₂₂))₃₃ or even macromolecules such as proteins. or even macromolecules such as proteins.

Coordination Number :

The coordination number of the central atom/ion is determined by the number of sigma bonds between The coordination number of the central atom/ion is determined by the number of sigma bonds between the ligands and the central atom/ions i.e. the number of ligand donor atoms to which the metal is directly the ligands and the central atom/ions i.e. the number of ligand donor atoms to which the metal is directly attached. Pi-bonds.

attached. Pi-bonds.

Some common co-ordination number of important metals are as given below. Some common co-ordination number of important metals are as given below.

M

Meettaall CCoooorrddiinnaattiioon n NNuummbbeerr MMeettaall CCoooorrddiinnaattiioon n NNuummbbeerr Cu Cu++ 22,, 44 NNii2+2+ 4, 4, 66 Ag Ag++ 22 FeFe2+2+ 4, 4, 66 Au Au++ 22,, 44 FFee3+3+ 66 Hg Hg₂₂2+2+ 22 CoCo2+2+ 4, 4, 66 Cu Cu2+2+ 44,, 66 CCoo3+3+ 66 Ag Ag2+2+ 44 AlAl3+3+ 66 Pt Pt2+2+ 44 ScSc3+3+ 66 Pd Pd2+2+ 44 PtPt4+4+ 66 Mg Mg2+2+ ₆₆ _Pd_Pd4+4+ ₆₆

(3)

Page No. # 2 Page No. # 2 Table : Common Monodentate Ligands

Table : Common Monodentate Ligands

C

CoommmmoonnNNaammee IIUUPPAACCNNaammee FFoorrmmuullaa

m

meetthhyyl l iissooccyyaanniiddee mmeetthhyylliissooccyyaanniiddee CCHH₃₃NCNC ttrriipphheennyyl pl phhoosspphhiinnee ttrriipphheenny l py l phhoosspphhiinnee//ttrriipphheennyyl pl phhoos ps phhaannee PPPPhh₃₃ p

pyyrriiddiinnee ppyyrriiddiinnee CC₅₅HH₅₅N (py)N (py) a

ammmmoonniiaa aammmmiinnee NNHH₃₃ m

meetthhyyl l aammiinnee mmeetthhyyllaammiinnee MMeeNNHH₂₂ w

waatteerr aaqquuaaoorraaqquuoo HH22OO c

caarrbboonnyyll ccaarrbboonnyyll CCOO tthhiiooccaarrbboonnyyll tthhiiooccaarrbboonnyyll CCSS n

niittrroossyyll nniittrroossyyll NNOO fflluuoorroo fflluuoorro o oor r fflluuoorriiddoo** FF – –

c

chhlloorroo cchhlloorro o oor r cchhlloorriiddoo** ClCl – –

b

brroommoo bbrroommo o oor r bbrroommiiddoo** BrBr – –

iiooddoo iiooddo o or or iiooddiiddoo** II – –

c

cyyaannoo ccyyaanniiddo o oor r ccyyaanniiddoo--CC* * ((CC--bboonnddeedd)) CNCN – –

iissooccyyaannoo iissooccyyaanniiddo o oor r ccyyaanniiddoo--NN* * ((NN--bboonnddeedd)) NCNC – –

tthhiiooccyyaannoo tthhiiooccyyaannaattoo--SS((SS--bboonnddeedd)) SCNSCN – –

iissootthhiiooccyyaannoo tthhiiooccyyaannaattoo--NN((NN--bboonnddeedd)) NCSNCS – –

c

cyyaannaatto o ((ccyyaannaattee)) ccyyaannaattoo--O O ((OO--bboonnddeedd)) OCNOCN – –

is

isoocyacyannaato to ((isisoocycyaannaatete)) cyacyannaatoto--N N ((NN--bboonnddeedd)) NCONCO – –

h

hyyddrrooxxoo hhyyddrrooxxo o oor r hhyyddrrooxxiiddoo** OHOH – –

n

niittrroo nniittrriittoo – –N (NN (N – –bonded)bonded) NONO₂₂ – –

n

niittrriittoo nniittrriittoo – –O (OO (O – –bonded)bonded) ONOONO – –

n

niittrraattee nniittrraattoo NNOO₃₃ – –

a

ammiiddoo aammiiddoo NNHH₂₂ – –

iimmiiddoo iimmiiddoo NHNH22 – –

n niittrriiddee nniittrriiddoo NN33 – – a azziiddoo aazziiddoo NN₃₃ – – h hyyddrriiddee hhyyddrriiddoo HH – – o oxxiiddee ooxxiiddoo OO22 – – p

peerrooxxiiddee ppeerrooxxiiddoo OO2222 – – s

suuppeerrooxxiiddee ssuuppeerrooxxiiddoo OO₂₂ – –

a

acceettaattee aacceettaattoo CCHH₃₃COOCOO – –

s

suullpphhaattee ssuullpphhaattoo SSOO₄₄22 – –

tthhiioossuullpphhaattee tthhiioossuullpphhaattoo SS22OO3322 – – s

suullpphhiittee ssuullpphhiittoo SSOO₃₃22 – –

h

hyyddrrooggeen n susullpphhiittee hhyyddrrooggeennssuullpphhiittoo HHSSOO₃₃ – –

s

suullpphhiiddee ssuullpphhiiddo o oor r tthhiioo SS22 – –

h

hyyddrrooggeen n ssuullpphhiiddee hhyyddrrooggeennssuullpphhiiddo o oor r mmeerrccaappttoo HSHS – –

tthhiioonniittrriittoo tthhiioonniittrriittoo (NOS)(NOS) – –

n

niittrroossyylliiuumm nniittrroossyylliiuum m oor r nniittrroossoonniiuumm NONO++ n

niittrroonniiuumm nniittrroonniiuumm NNOO22++ *

*The The 2004 I2004 IUPAC draft reUPAC draft recommcommends that anionic ligands will end with-ido.ends that anionic ligands will end with-ido.

ETOOS

(4)

Page No. # 3 Page No. # 3 Table : Common Chelating Amines

Table : Common Chelating Amines

Table : Common Multidentate (Chelating) Ligands Table : Common Multidentate (Chelating) Ligands

C

Coomm mm oon n NNaa mm e e IIUUPPAAC C NNaa mm ee AAbbbbrree vviiaa ttiioon n FFoorrmm uullaa SSttrruuccttuurree

acetylacetonato

acetylacetonato 2,4-pentanediono2,4-pentanediono_{or acetylacetonato}_{or acetylacetonato} aaccaacc CCHH33COCHCOCHCOCHCOCH33 – –

2

2,,22''--bbiippyyrriiddiinnee 22,,22''--bbiippyyrriiddyyll bbiippyy CC1010HH88NN22

1,10-phenanthroline/ 1,10-phenanthroline/ phenanthroline

phenanthroline 11, 1, 100--ddiiaam im innoopphheennaanntthhrreennee pphheenn, o, o--pphheenn CC1212HH88NN22

o

oxxaallaattoo ooxxaallaattoo ooxx CC22OO4422 – –

d

diiaallkkyyllddiitthhiiooccaarrbbaamm aattoo ddiiaallkkyyllccaarrbbaammooddiitthhiiooaattoo ddttcc SS22CNRCNR22 – –

1,2-bis(diphenylphophine)ethane

1,2-bis(diphenylphophine)ethane 1,2-ethanediylbis1,2-ethanediylbis_{(dipheylphosphene)}_{(dipheylphosphene)} ddppppee PPhh22PCPC22HH44PPPP hh22

o-phenylenebis o-phenylenebis (dimethylarsine) (dimethylarsine) 1,2-phenylenebis 1,2-phenylenebis (dimethylarsene)

(dimethylarsene) ddiiaarrss CC66HH44(As(CH(As(CH33))22))22

dimethylglyoximato

dimethylglyoximato butanedienedioximebutanedienedioxime_{or dimethylglyoximato}_{or dimethylglyoximato} DDMM GG HHOONNCC((CCHH33)C(CH)C(CH33)NO)NO – –

ethylenediaminetetraacetato ethylenediaminetetraacetato 1,2-ethanediyl 1,2-ethanediyl (dinitrilo)tetraacetato (dinitrilo)tetraacetato or ethylenediaminetetraacetato or ethylenediaminetetraacetato E EDDTTAA (( – – OOCCH

OOCCH22))22NCHNCH22CHCH22N(CHN(CH22COOCOO – –))22

pyrazolylborato

pyrazolylborato hydrotris-hydrotris-_{(pyrazo-1-yl)borato}_{(pyrazo-1-yl)borato}

— — O C O CHH22CC — — O C O CHH22CC C H C O C H C O22 — — C H C O C H C O22 — — || || O O || || || || O O O O || || O O : : : : ETOOS

(5)

Nomenclature of Coordination Compounds

Writing the name of Mononuclear Coordination Compounds : Writing the name of Mononuclear Coordination Compounds : The following rules are followed when naming coordination compounds : The following rules are followed when naming coordination compounds : Names of the anionic ligands end in

Names of the anionic ligands end in – –o. Anionic ligands ending witho. Anionic ligands ending with ‘‘ideide’’ are named are named by replacingby replacing ‘‘ideide’’

by suffix by suffix ‘‘idoido’’..

e e..gg . . SSyymmbbooll NNaammee N N33 – – _Nitrido_Nitrido Cl Cl ¯ ¯ ChloridoChlorido O O₂₂22 – – _Peroxido_Peroxido Br Br ¯ ¯ BromidoBromido O O₂₂HH ¯ ¯ PerhydroxidoPerhydroxido CN CN ¯ ¯ CyanidoCyanido S S22 – – _Sulphidido_Sulphidido O O22 – – _Oxido_Oxido NH NH22 – – _Amidido_Amidido OH OH ¯ ¯ HydroxidoHydroxido Ligands whose names end in

Ligands whose names end in ‘‘iteite’’ oror ‘‘ateate’’ become become ‘‘itoito’’ oror ‘‘atoato’’ i.e., by replacing the ending i.e., by replacing the ending ‘‘ee’’

with

with ‘‘oo’’ as follows as follows

S Syymmbbooll NNaamme e aas s lliiggaanndd CO CO₃₃22 – – _Carbonato_Carbonato C C₂₂OO₄₄22 – – _Oxalato_Oxalato SO SO₄₄22 – – _Sulphato_Sulphato NO NO₃₃ ¯ ¯ NitratoNitrato SO SO₃₃22 – – _Sulphito_Sulphito CH

CH₃₃COOCOO ¯ ¯ AcetatoAcetato NO

NO₂₂ ¯ ¯ (b(bonondeded td thrhrououggh oh oxyxyggenen) n) nititririte te (b(bonondded ed ththrorouugh gh ninitrtrogogenen) n) niitrtroo Neutral ligands are given the same names at the neutral molecules. For example. Ethylene diamine as Neutral ligands are given the same names at the neutral molecules. For example. Ethylene diamine as a ligand is named ethylene diamine in the complex. However some exceptions to this rule are

a ligand is named ethylene diamine in the complex. However some exceptions to this rule are A Aqquuoo HH₂₂OO A Ammmmiinnee NNHH₃₃ C Caarrbboonnyyll CCOO N Niittrroossyyll NNOO T

Thhiiooccaarrbboonnyyll CCSS tteettrraapphhoosspphhoorruuss PP₄₄ d

diiooxxyyggeenn OO₂₂ o

occttaassuullpphhuurr SS₈₈ u

urreeaa CCOO((NNHH₂₂))₂₂ Names of positive ligands ends in

Names of positive ligands ends in ‘‘iumium’’ e.g. e.g.

NO

NO++ Nitrosylium Nitrosylium NH

NH₂₂NHNH₃₃++ Hydrazinium Hydrazinium

ETOOS

(6)

Page No. # 5 Page No. # 5 Prefixes mono, di, tri, etc., are used to indicate the number of the one kind of ligands in the Prefixes mono, di, tri, etc., are used to indicate the number of the one kind of ligands in the coordination entity

coordination entity. When . When the names of the the names of the ligands include a numerical prefix or are ligands include a numerical prefix or are complicatedcomplicated or whenever the use of normal prefixes creates some confusion, it is set off in parentheses or whenever the use of normal prefixes creates some confusion, it is set off in parentheses and the second set of prefixes is used.

and the second set of prefixes is used. 2

2 ddii bbiiss 3

3 ttrrii ttrriiss 4

4 tteettrraa tteettrraakkiiss 5

5 ppeennttaa ppeennttaakkiiss 6

6 hheexxaa hheexxaakkiiss 7

7 hheeppttaa hheeppttaakkiiss Examples ;

Examples ; [CoCl[CoCl₂₂(NH(NH₂₂CHCH₂₂CHCH₂₂NHNH₂₂))₂₂]]++, dichloridobis(ethane-1,2-diamine)cobalt(III)., dichloridobis(ethane-1,2-diamine)cobalt(III). [NiCl

[NiCl₂₂(PPh(PPh₃₃))₂₂], ], dichloridobdichloridobis(triphenyis(triphenylphosphine)nlphosphine)nickel(II).ickel(II).

Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman Oxidation state of the metal in cation, anion or neutral coordination entity is indicated by Roman numeral in the parentheses after the name of metal.

numeral in the parentheses after the name of metal.

If the complex ion is a cation, the metal is named same as the element. For example, Co If the complex ion is a cation, the metal is named same as the element. For example, Co in a complex cation is called cobalt and Pt is called platinum. If the complex ion is an anion, in a complex cation is called cobalt and Pt is called platinum. If the complex ion is an anion, the name of the metal ends with the suffix - ate. For example, Co in a complex anion, [Co(SCN) the name of the metal ends with the suffix - ate. For example, Co in a complex anion, [Co(SCN)₄₄]]22 – –

is called cobaltate. For some metals, the Latin names are used in the complex anions. is called cobaltate. For some metals, the Latin names are used in the complex anions.

iirroon n ((FFee)) ffeerrrraattee lleeaad d ((PPbb)) pplluummbbaattee s

siillvveer r ((AAgg)) aarrggeennttaattee ttiin n ((SSnn)) ssttaannnnaattee g

goolld d ((AAuu)) aauurraattee Examples ;

Examples ; [Co(NH[Co(NH₃₃))₄₄ClCl₂₂]]++, pentaamminechloridocobalt(III)., pentaamminechloridocobalt(III). (NH

(NH₄₄))₂₂ [Co(SCN) [Co(SCN)₄₄], ammonium ], ammonium tetrathiocyantetrathiocyanato-S-cobaltate(II).ato-S-cobaltate(II). The neutral complex molecule is named similar to that of the complex cation. The neutral complex molecule is named similar to that of the complex cation. Example ;

Example ; [CrCl[CrCl₃₃(py)(py)₃₃], trichloridotris(pyridine)chromium(III).], trichloridotris(pyridine)chromium(III).

BONDING IN COORDINATION COMPOUNDS :

Werner's Theory :

Alfred Werner (considered as the father of coordination chemistry) studied the structure of coordination Alfred Werner (considered as the father of coordination chemistry) studied the structure of coordination complexes such as CoCl

complexes such as CoCl₃₃. 6NH. 6NH₃₃ and CuSO and CuSO₄₄. 4NH. 4NH₃₃ in 1893. According to him- in 1893. According to him-(a) Each metal in coordination compound possesses two types of valencies : (a) Each metal in coordination compound possesses two types of valencies :

((ii)) prprimaimary ry vavalelencncy y or or prprinincicipapal l vavalelencncieies os or r ioioninisasablble ve valalenencicieses.. (i

(ii)i) SeSecocondndarary y vavalelencncy y or or nononiniononisisabable le vavalelencncieiess (b) Primary valencies are satisfied by anions only

(b) Primary valencies are satisfied by anions only. The num. The number of primber of primary valencies depends upon theary valencies depends upon the oxidation state of the central metal. It may change from one compound to other. These are represented oxidation state of the central metal. It may change from one compound to other. These are represented by dotted lines between central metal atom and anion.

by dotted lines between central metal atom and anion.

(c) Secondary valencies are satisfied only by electron pair donor, the ions or the neutral species. These (c) Secondary valencies are satisfied only by electron pair donor, the ions or the neutral species. These

are represented by thick lines. are represented by thick lines.

(d) Each metal has a fixed number of secondary valencies also referred as coordination number. The (d) Each metal has a fixed number of secondary valencies also referred as coordination number. The coordination number depends mainly on the size and the charge on the central atom. The maximum coordination number depends mainly on the size and the charge on the central atom. The maximum number of ions or molecules that the central atom can hold by secondary valencies is known as number of ions or molecules that the central atom can hold by secondary valencies is known as coordination number.

coordination number.

(e) The ions attached to primary valencies possess ionising nature whereas the ions attached to secondary (e) The ions attached to primary valencies possess ionising nature whereas the ions attached to secondary

valencies do not ionise when the complex is dissolved in a solvent. valencies do not ionise when the complex is dissolved in a solvent.

(f) Every central ion tends to satisfy its primary as well as secondary valencies. (f) Every central ion tends to satisfy its primary as well as secondary valencies.

(g) The secondary valencies are directional and are directed in space about the central metal ion. The (g) The secondary valencies are directional and are directed in space about the central metal ion. The primary valencies are non-directional. The presence of secondary valencies gives rise to stereoisomerism primary valencies are non-directional. The presence of secondary valencies gives rise to stereoisomerism in complexes.

in complexes.

ETOOS

(7)

Effective Atomic Number Rule given by Sidgwick :

It can be defined as

It can be defined as the resultant the resultant number of electrons with the metal anumber of electrons with the metal atom or ion after gaining eletom or ion after gaining electronsctrons from the donor atoms of the ligands.

from the donor atoms of the ligands.

Effective Atomic Number (EAN) = No. of electron present on the metal ato

Effective Atomic Number (EAN) = No. of electron present on the metal ato m/ion + No. of electronsm/ion + No. of electrons donated by ligands to it.

donated by ligands to it. O ORR

Effective Atomic Number (EAN) = Atomic no. of central metal

Effective Atomic Number (EAN) = Atomic no. of central metal – – Oxidation state of central metal Oxidation state of central metal + No. of electrons donated by ligands.

+ No. of electrons donated by ligands.

The complexes in which the EAN of the central atom equals the atomic number of the next noble gas, The complexes in which the EAN of the central atom equals the atomic number of the next noble gas, are found to be extra stable.

are found to be extra stable.

Valence bond theory :

The salient features of the theory are summarised below. The salient features of the theory are summarised below.

(a) The central metal ion has a number of empty orbitals for accommodating electrons donated by the (a) The central metal ion has a number of empty orbitals for accommodating electrons donated by the ligands. The number of empty orbitals is equal to the coordination number of the metal ion for the particular ligands. The number of empty orbitals is equal to the coordination number of the metal ion for the particular complex.

complex.

(b) The atomic

(b) The atomic orbitals (s, p or orbitals (s, p or d) of the md) of the m etal ion hybridize to form hybrid orbitals with definite directionaletal ion hybridize to form hybrid orbitals with definite directional properties. These hybrid orbitals now overlap with the ligand orbitals to form strong chemical bonds. properties. These hybrid orbitals now overlap with the ligand orbitals to form strong chemical bonds. (c) The d-orbitals involved in the hybridization may be either inner (n

(c) The d-orbitals involved in the hybridization may be either inner (n – –1) d orbitals or outer n d-orbitals.1) d orbitals or outer n d-orbitals.

The complexes f

The complexes formed in these two ormed in these two ways are referred to as ways are referred to as low spin and high spin comlow spin and high spin complexes, respectivelyplexes, respectively.. (d) Each ligand contains a lone pair of electrons.

(d) Each ligand contains a lone pair of electrons.

(e) A covalent bond is formed by the overlap of a vacant hybridized metal orbital and a filled orbital of (e) A covalent bond is formed by the overlap of a vacant hybridized metal orbital and a filled orbital of the ligand. The bond is also sometimes called as a coordinate bond.

the ligand. The bond is also sometimes called as a coordinate bond.

(f) If the complex contains unpaired electrons, it is paramagnetic in nature, while if it does not contain (f) If the complex contains unpaired electrons, it is paramagnetic in nature, while if it does not contain unpaired electrons, it is diamagnetic in nature.

unpaired electrons, it is diamagnetic in nature.

Co-ordination numbers, Hybridised orbitals and geometry of some co-ordination compounds Co-ordination numbers, Hybridised orbitals and geometry of some co-ordination compounds

C

Coooorrddiinnaattiioon n HHyybbrriiddiisseed d oorrbbiittaall GGeeoommeettrriiccaal l sshhaappe e ooff EExxaammppllees s ooff N

Nuummbbeerr tthhee ccoommpplleexx ccoommpplleexx 2

2 sspp [[AAgg((NNHH₃₃))₂₂]]++ L

Liinneeaarr [[AAgg((CCNN))₂₂]] ¯ ¯

3 3 spsp22 [Hg[Hg## 3 3 ¯ ¯ ]] 4 4.. sspp33 [FeCl[FeCl₄₄]] ¯ ¯ [Ni(CO) [Ni(CO)₄₄]]00 Zn(NH Zn(NH₃₃))₄₄+2+2 [ZnCl [ZnCl₄₄]] – –22_,[CuX_,[CuX 4 4]] – –22 where X = CN where X = CN ¯ ¯ Cl Cl ¯,Br¯, ¯,Br¯, ## ¯, ¯, CNSCNS dsp dsp22 ETOOS

(8)

Page No. # 7 Page No. # 7 T

Thhe e dd--oorrbbiittaal l iinnvvoollvveed d iiss [[NNii((CCNN))₄₄]] – –22

4.

4. dd_x_x22_–_–_yy22 o orrbbiittaall [[PPtt((NNHH₃₃))₄₄]]+2+2 of the inner shell, i.e. it

of the inner shell, i.e. it is (n

is (n – – 1)d1)d_x_x22_–_–_yy22 orbitalorbital

dsp

dsp33 [CuCl[CuCl₅₅]] – –33

5

5.. TThhee dd--oorrbbiittaall iiss [[MMooCCll₅₅]]00 (n - 1)d

(n - 1)d_z_z22 o orrbbiittaall [[FFee((CCOO))₅₅]]00

sp sp33dd 5

5.. TThhe e dd--oorrbbiittaal l iis s nndd_x_x22_–_–_yy22 [SbF[SbF₅₅]] – –22 IFIF₅₅ orbital orbital Square pyramidal Square pyramidal d d22spsp33

When d-orbitals are (n-1) When d-orbitals are (n-1) d

d--oorrbbiittaalls s ((IInnnneer r oorrbbiittaall [[CCrr((NNHH₃₃))₆₆+3+3]] 6

6.. ccoommpplleexxeess) ) oorr sspp33_d_d22 _[Ti(H_[Ti(H 2 2O)O)66]]+3+3 W

Whheenn dd--oorrbbiittaallss aarree [[FFee((CCNN))₆₆]] – –22

n

nd d oorrbbiittaal l ((OOuutteer r oorrbbiittaall [[CCoo((NNHH₃₃))₆₆]]+3+3 c

coommpplleexxeess) ) IIn n bbootth h cacasseess [[PPttCCll₆₆]] – –22_[CoF_[CoF

6 6]] – –33 p-orbitals are d

p-orbitals are d_z_z2₂ and d and d_x_x2_2-y_-y2₂ orbitals.

orbitals.

Octahedral Octahedral

Crystal Field Theory :

The drawbacks of VBT of

The drawbacks of VBT of coordination compounds are, to a considerable extent, remcoordination compounds are, to a considerable extent, rem oved by the Crystaloved by the Crystal Field Theory.

Field Theory.

The crystal field theory

The crystal field theory (CFT) is an electrostatic model which considers the metal-lig(CFT) is an electrostatic model which considers the metal-ligand bond to be and bond to be ionicionic arising purely from electrostatic interaction between the metal ion and the ligand. Ligands are treated as arising purely from electrostatic interaction between the metal ion and the ligand. Ligands are treated as point charges in case of anions or dipoles in case of neutral molecules. The five d orbitals is an isolated point charges in case of anions or dipoles in case of neutral molecules. The five d orbitals is an isolated gaseous metal atom/ion have same energy, i.e., they are degenerate. This degeneracy is maintained if gaseous metal atom/ion have same energy, i.e., they are degenerate. This degeneracy is maintained if a spherically symmetrical field of negative charges surrounds the metal atom/ion. However, when this negative a spherically symmetrical field of negative charges surrounds the metal atom/ion. However, when this negative field is due to ligands (either anions or the negative ends of dipolar molecules like NH

field is due to ligands (either anions or the negative ends of dipolar molecules like NH₃₃ and H and H₂₂O) in aO) in a complex, it becomes asymmetrical and the degeneracy of the d orbitals is lost. It results in splitting of complex, it becomes asymmetrical and the degeneracy of the d orbitals is lost. It results in splitting of the d orbitals. The pattern of spitting depends upon the nature of the crystals field.

the d orbitals. The pattern of spitting depends upon the nature of the crystals field.

ETOOS

(9)

Page No. # 8 Page No. # 8 Crystal field splitting in octahedral coordination entities :

Crystal field splitting in octahedral coordination entities :

Figure showing crystal field splitting in octahedral complex. Figure showing crystal field splitting in octahedral complex.

In general, ligands can be arranged in a series in the orders of increasing field strength as given below: In general, ligands can be arranged in a series in the orders of increasing field strength as given below: II – – _<_{< Br}_Br – –_{< SCN}_{< SCN} – – _<_{< Cl}_Cl – – _{< S}_<_S22 – – _<_{< F}_F – – _<_{< OH}_OH – – _<_{< C}_C

2

2OO4422 – – < < HH22O < NCSO < NCS – – < edta < edta44 – – < < NHNH33 < en < NO < en < NO22 – – << CN

CN – – _<_{< CO}_CO

The two possibilites are : The two possibilites are : (i) If

(i) If $$ 0

0 < P, the fourth electron enters one of the e < P, the fourth electron enters one of the egg orbitals giving the configuration t orbitals giving the configuration t332g2geegg11. Ligands for. Ligands for which

which $$ 0

0 < P are known as weak field ligands and form high spin complexes. < P are known as weak field ligands and form high spin complexes. (ii) If

(ii) If $$ 0

0 > P, it becomes more energetically favourable for the fourth electron to occupy a t > P, it becomes more energetically favourable for the fourth electron to occupy a t2g2g orbital with orbital with configuration t

configuration t_2g_2g44_e_e g

g00. Ligands which produce this effect are known as strong field ligands and form low. Ligands which produce this effect are known as strong field ligands and form low spin complexes.

spin complexes.

Crystal field splitting in tetrahedral coordination entities : Crystal field splitting in tetrahedral coordination entities :

Figure showing crystal field splitting in tetrahedral complex. Figure showing crystal field splitting in tetrahedral complex. $

$

tt << $$oo

ETOOS

(10)

Page No. # 9 Page No. # 9 Crystal field splitting in square planar coordination entities :

Crystal field splitting in square planar coordination entities :

$ $

sp

sp = 1.3 = 1.3 $$oo..

COLOUR IN COORDINATION COMPOUNDS :

Relationship between the wavelength of light absorbed and the colour observed In some coordination entitles Relationship between the wavelength of light absorbed and the colour observed In some coordination entitles

Table Table

–––

–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––

C

Coooorrddiinnaattiioon n eennttiittyy WaWavveelleennggtth h oof lf liigghhtt CCoolloouur r oof f lliigghhtt CCoolloouur r oof f ccoooorrddiinnaattiioonn a

abbssoorrbbeed d ((nnmm)) ababssoorrbbeedd eennttiittyy

–––

–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––

[CoCl(HN

[CoCl(HN₃₃))₅₅]]2+2+ 553355 YYeellllooww VViioolleett [Co(NH

[Co(NH₃₃))₅₅(H(H₂₂O)]O)]3+3+ 505000 BBlluuee GGrreeeenn RReedd [Co(NH

[Co(NH₃₃))₆₆]]3+3+ 447755 BlluBuee YYeelllloowwOOrraannggee [Co(CN)

[Co(CN)₆₆]]3-3- 331100 UUllttrraavviioolleett PPaalle e YYeellllooww [Cu(H

[Cu(H₂₂O)O)₄₄]]2+2+ 606000 RReedd BBlluuee [Ti(H

[Ti(H₂₂O)O)₆₆]]3+3+ ₄₄₉₉₈₈ _Y_Ye_ellllo_ow_w_G_Grre_ee_en_n _P_Pu_urrp_plle_e

––– –––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––

ISOMERISM :

STRUCTURAL ISOMERISM :

((AA)) IIoonniissaattiioon in issoommeerriissm :m : This type of isomerism occurs

This type of isomerism occurs when the counter ion in a when the counter ion in a coordinatiocoordination compound is itself a n compound is itself a potential ligandpotential ligand and can displace a

and can displace a ligand which ligand which can then become the counter ion. can then become the counter ion. For example, For example, following complexesfollowing complexes show ionisation isomerism.

show ionisation isomerism. [Co(NH

[Co(NH₃₃))₅₅SOSO₄₄]NO]NO₃₃ and [Co(NHand [Co(NH₃₃))₅₅NONO₃₃]SO]SO₄₄ [Co(NH

[Co(NH₃₃))₄₄(NO(NO₂₂)Cl]Cl and [Co(NH)Cl]Cl and [Co(NH₃₃))₄₄ClCl₂₂]NO]NO₂₂.. [Co(NH

[Co(NH₃₃))₄₄(H(H₂₂O)Cl]BrO)Cl]Br₂₂ and [Co(NH and [Co(NH₃₃))₄₄BrCl]Br.HBrCl]Br.H₂₂O. [Also an example of hydrate isomers.]O. [Also an example of hydrate isomers.] [Pt(NH

[Pt(NH₃₃))₄₄ClCl₂₂]Br]Br₂₂, and [Pt(NH, and [Pt(NH₃₃))₄₄BrBr₂₂]Cl]Cl₂₂.. [CoCl(en)

[CoCl(en)₂₂(NO(NO₂₂)]SCN, [Co(en))]SCN, [Co(en)₂₂(NO(NO₂₂)SCN]Cl and [Co(en))SCN]Cl and [Co(en)₂₂(SCN)Cl]NO(SCN)Cl]NO₂₂

ETOOS

(11)

Page No. # 10 Page No. # 10 ((BB)) SSoolvlvaate te / / hhyydrdraate te isisomomeerirism sm ::

It occurs when water forms a part of the coordination entity or is outside it. This is similar to ionisation It occurs when water forms a part of the coordination entity or is outside it. This is similar to ionisation isomerism. Solvate isomers differ by whether or not a solvent molecule is directly bonded to the metal isomerism. Solvate isomers differ by whether or not a solvent molecule is directly bonded to the metal ion or merely present as free solvent molecules in the crystal lattice. For example, CrCl

ion or merely present as free solvent molecules in the crystal lattice. For example, CrCl₃₃ . . 6H6H₂₂O existsO exists in three distinct isomeric forms : [Cr(H

in three distinct isomeric forms : [Cr(H₂₂O)O)₆₆]Cl]Cl₃₃, violet ; [CrCl(H, violet ; [CrCl(H₂₂O)O)₅₅]Cl]Cl₂₂.H.H₂₂O, blue green : [CrClO, blue green : [CrCl₂₂(H(H₂₂O)O)₄₄]Cl.2H]Cl.2H₂₂O,O, dark green. These three cationic isomers can be separated by cation ion exchange from commercial CrCl

dark green. These three cationic isomers can be separated by cation ion exchange from commercial CrCl₃₃.6H.6H₂₂O.O. A fourth isomer [Cr(H

A fourth isomer [Cr(H₂₂O)O)₃₃ClCl₃₃], yellow ], yellow green also occurs at high concentration of HClgreen also occurs at high concentration of HCl. . Apart from theirApart from their distinctive colours, the three isomers can be identified by the addition of excess of aqueous silver nitrate distinctive colours, the three isomers can be identified by the addition of excess of aqueous silver nitrate to their aqueous solutions, which

to their aqueous solutions, which precipitates chloride in the molar ratio of precipitates chloride in the molar ratio of 3 : 2 : 1 respectively3 : 2 : 1 respectively.. C

Coommpplleexx RReeaaccttiioon n wwiitth h AAggNNOO₃₃ Reaction with conc. HReaction with conc. H₂₂SOSO₄₄(dehydrating agent)(dehydrating agent) [Cr(H

[Cr(H₂₂O)O)₆₆]Cl]Cl₃₃ iin tn the he momolalar rr ratatiio oo of 3f 3::11 No No wawateter mor mollececulule ie is ls losost ot or nr no ro reaeactctioionn [CrCl(H

[CrCl(H₂₂O)O)₅₅]Cl]Cl₂₂.H.H₂₂OO iin n tthhe e mmoollaar rr raattiio o oof 2f 2::11 oonne me moolle e oof wf waatteer r iis ls loosst t ppeer mr moolle oe of cf coom pm plleexx [CrCl

[CrCl₂₂(H(H₂₂O)O)₄₄]Cl.2H]Cl.2H₂₂OO iin tn thhe me moollaar rr raatitio oo of 1f 1::11 ttwwo mo moolle e of of wwaatteer ar arre e lloosst t pper er momolle oe of cf coompmplleexx Other examples are :

Other examples are : [Co(NH

[Co(NH₃₃))₄₄(H(H₂₂O)Cl]ClO)Cl]Cl₂₂ aanndd [[CCoo((NNHH₃₃))₄₄ClCl₂₂]Cl.H]Cl.H₂₂OO [Co(NH

[Co(NH₃₃))₅₅(H(H₂₂O)](NOO)](NO₃₃))₃₃ aanndd [[CCoo((NNHH₃₃))₅₅(NO(NO₃₃)](NO)](NO₃₃))₂₂.H.H₂₂O.O. ((CC)) LLiinnkkaagge e iissoommeerriissm m ::

In some ligands, like ambidentate ligands, there are two possible coordination sites. In such cases, linkage In some ligands, like ambidentate ligands, there are two possible coordination sites. In such cases, linkage isomerism exist. e.g.,NO

isomerism exist. e.g.,NO₂₂ group can be bonded to metal ions through nitrogen ( group can be bonded to metal ions through nitrogen ( – –NONO₂₂) or through ) or through oxygenoxygen

(( – –ONO). SCN too can be bonded through sulphur (ONO). SCN too can be bonded through sulphur ( – –SCN) thiocyanate or through nitrogen (SCN) thiocyanate or through nitrogen ( – –NCS)NCS)

isothiocyanate. isothiocyanate. For example :

For example : [Co(ONO)(NH [Co(ONO)(NH₃₃))₅₅] ] ClCl₂₂ & [Co(NO & [Co(NO₂₂)) (NH(NH₃₃))₅₅] ] ClCl₂₂ .. ((DD)) CCoooorrddiinnaattiioon n iissoommeerriissm :m :

Coordination compounds made up of cationic and anionic coordination entities show this type of isomerism Coordination compounds made up of cationic and anionic coordination entities show this type of isomerism due to the interchange of ligands between the cation and anion entities. Some of the examples are : due to the interchange of ligands between the cation and anion entities. Some of the examples are : ((ii)) [[CCoo((NNHH₃₃))₆₆][Cr(CN)][Cr(CN)₆₆] and [Cr(NH] and [Cr(NH₃₃))₆₆](Co(CN)](Co(CN)₆₆]]

((iiii)) [[CCuu((NNHH₃₃))₄₄][PtCl][PtCl₄₄] and [Pt(NH] and [Pt(NH₃₃))₄₄][CuCl][CuCl₄₄]]

((iiiiii)) [[CCoo((NNHH₃₃))₆₆][Cr(SCN)][Cr(SCN)₆₆] and [Cr(NH] and [Cr(NH₃₃))₄₄(SCN)(SCN)₂₂][Co(NH][Co(NH₃₃))₂₂(SCN)(SCN)₄₄]] ((iivv)) [[PPtt((NNHH₃₃))₄₄][PtCl][PtCl₆₆] and [Pt(NH] and [Pt(NH₃₃))₄₄ClCl₂₂][PtCl][PtCl₄₄]]

Such isomers are expected to have significant differences in their physical and chemical properties. Such isomers are expected to have significant differences in their physical and chemical properties. ((EE)) LLiiggaannd d iissoommeerriissm m ::

Since many ligands are organic compounds which have possibilities for isomerism, the resulting com

Since many ligands are organic compounds which have possibilities for isomerism, the resulting com plexesplexes can show isomerism from this source.

can show isomerism from this source.

For example ; ligands 1,2-diaminopropane(propylenediamine or

For example ; ligands 1,2-diaminopropane(propylenediamine or pn)pn) an andd 1,3-diaminopropane(trimethylenediamine or

1,3-diaminopropane(trimethylenediamine or tntn) are such pairs. Sim) are such pairs. Sim ilarly ortho-, meta- and para-toluidineilarly ortho-, meta- and para-toluidine (CH

(CH₃₃CC₆₆HH₄₄NHNH₂₂).).

((FF)) PPoollyymmeerriissaattiioon in issoommeerriissm :m :

Considered to be a special case of coordination isomerism, in this the various isomers differ in formula Considered to be a special case of coordination isomerism, in this the various isomers differ in formula weight from one another

weight from one another, so not true , so not true isomers in real sense. For example [Co(NHisomers in real sense. For example [Co(NH₃₃))₄₄(NO(NO₂₂))₂₂][Co(NH][Co(NH₃₃))₂₂(NO(NO₂₂))₄₄],], [Co(NH

[Co(NH₃₃))₆₆][Co(NO][Co(NO₂₂))₆₆], ], [Co(NH[Co(NH₃₃))₅₅(N(N OO₂₂)][Co(NH)][Co(NH₃₃))₂₂(N(N OO₂₂))₄₄]]₂₂, , [Co(NH[Co(NH₃₃))₆₆][Co(NH][Co(NH₃₃))₂₂(N(N OO₂₂))₄₄]]₃₃,, [Co(NH

[Co(NH₃₃))₄₄(NO(NO₂₂))₂₂]]₃₃[Co(NO[Co(NO₂₂))₆₆] and [Co(NH] and [Co(NH₃₃))₅₅(NO(NO₂₂))₂₂]]₃₃[Co(NO[Co(NO₂₂))₆₆]]₂₂. These all have the empirical formula. These all have the empirical formula Co(NH

Co(NH₃₃))₃₃(NO(NO₂₂))₃₃, but they have formula weights that are 2,2,3,4,4 and 5 times this, respectively., but they have formula weights that are 2,2,3,4,4 and 5 times this, respectively.

ETOOS

(12)

Stereoisomerism

Geometrical Isomerism

This type of isomerism

This type of isomerism arises in heteroleptic complexes due to arises in heteroleptic complexes due to different possible geometric arrangementsdifferent possible geometric arrangements of the ligands. Geometrical isomerism is common among coordination compounds with coordination numbers of the ligands. Geometrical isomerism is common among coordination compounds with coordination numbers 4 and 6.

4 and 6.

Coordination Number Four : Coordination Number Four : Tetrahedral Complex :

Tetrahedral Complex :

The tetrahedral compounds can not show geometrical isomerism as we all know that all four positions The tetrahedral compounds can not show geometrical isomerism as we all know that all four positions are equivalent in

are equivalent in tetrahedral geometry.tetrahedral geometry. Square Planar Complex :

Square Planar Complex :

In a square planar complex of formula [Ma

In a square planar complex of formula [Ma₂₂bb₂₂] [a and b ] [a and b are unidentate], the two ligandsare unidentate], the two ligands‘‘aa’’ may be arranged may be arranged

adjacent to each other in a cis isomer, or opposite to each other in a trans isomer as depicted. adjacent to each other in a cis isomer, or opposite to each other in a trans isomer as depicted.

Coordination Number Six : Coordination Number Six :

Geometrical isomerism is also possible in octahedral complexes. Geometrical isomerism is also possible in octahedral complexes.

Optical Isomerism :

A coordination compound which can rotate the plane of p

A coordination compound which can rotate the plane of p olarised light is said to be optically active.olarised light is said to be optically active. When the coordination compounds have same formula but differ in their ability to rotate directions When the coordination compounds have same formula but differ in their ability to rotate directions of the plane of polarised light are said to exhibit optical isomerism and the molecules are optical of the plane of polarised light are said to exhibit optical isomerism and the molecules are optical isomers. Optical isomers are mirror images that cannot be superimposed on one another. These are isomers. Optical isomers are mirror images that cannot be superimposed on one another. These are called as enantiomers.

called as enantiomers. Octahedral complex : Octahedral complex :

Optical isomerism is common in octahedral complexes involving didentate ligands. For example, Optical isomerism is common in octahedral complexes involving didentate ligands. For example, [Co(en)

[Co(en)₃₃]]3+3+ has d and has d and !!_{forms as given below.}_{forms as given below.}

d and

d and !!_{of [Co(en)}_{of [Co(en)}

3 3]]3+3+ Cis-isomer of [PtCl

Cis-isomer of [PtCl₂₂(en)(en)₂₂]]2+2+ show optical isomerism as show optical isomerism as shown below because of the absence of planeshown below because of the absence of plane of symmetry as well as centre of symmetry.

of symmetry as well as centre of symmetry.

ETOOS

(13)

Page No. # 12 Page No. # 12 d and

d and !!_{of cis-[PtCl}_{of cis-[PtCl}

2

2(en)(en)22]]2+2+ But trans isomer of [PtCl

But trans isomer of [PtCl₂₂(e(enn₂₂)])]2+2+ does not show optical isomerism. does not show optical isomerism.

Tetrahedral complex : Tetrahedral complex :

Optical isomerism is expected in tetrahedral complexes of the type [Mabcd] analogous to tetrahedral Optical isomerism is expected in tetrahedral complexes of the type [Mabcd] analogous to tetrahedral carbon atom.

carbon atom.

Organometallic compounds :

Bonding in Metal Carbonyls

The metal

The metal – –carbon bond in metal carbonyls possess both s and p character. The Mcarbon bond in metal carbonyls possess both s and p character. The M——CC %% bond is formed bond is formed

by the donation of lone pair of electrons on the carbonyl carbon

by the donation of lone pair of electrons on the carbonyl carbon (CO is a weak base) into a vacant orbital(CO is a weak base) into a vacant orbital of the metal. The M

of the metal. The M —— CC && bond is formed by the donation of a pair of electrons from a filled d orbital bond is formed by the donation of a pair of electrons from a filled d orbital

of metal into the vacant antibonding

of metal into the vacant antibonding&&_{* orbital of carbon monoxide. Thus carbon monoxide acts as}_{* orbital of carbon monoxide. Thus carbon monoxide acts as}%%_donor_donor (OC

(OC""_{M) and a}_{M) and a}&&_{acceptor (OC}_{acceptor (OC} ''_{M), with the two interactions creating a synergic effect which strengthens}_{M), with the two interactions creating a synergic effect which strengthens} the

the bond between bond between CO and the CO and the metal as shown imetal as shown in figure.n figure.

M M CC OO " " " " " " " " & & & & & & % % ( ( Synergic bonding Synergic bonding (i) As M

(i) As M —— C C && bonding increases, the C bonding increases, the C —— O bond becomes weaken. The greater the positive charge O bond becomes weaken. The greater the positive charge

on the central metal atom, the less readily the metal can donate electron density into the

on the central metal atom, the less readily the metal can donate electron density into the&&_{* orbitals of}_{* orbitals of} the carbon monoxide ligands to weaken the C

the carbon monoxide ligands to weaken the C —— O bond. O bond.

(ii) In contrast, in the anionic complex (i.e. carbonylate anion) the metal has a greater electron density (ii) In contrast, in the anionic complex (i.e. carbonylate anion) the metal has a greater electron density to be dispersed, with the result that M

to be dispersed, with the result that M —— CC && bonding is enhanced and the C bonding is enhanced and the C —— O bond is diminished O bond is diminished

in strength. For example ; in isoelectronic complexes the strength of metal-ligand bond increases and in strength. For example ; in isoelectronic complexes the strength of metal-ligand bond increases and strength of C

strength of C —— O bond in CO decreases (because bond order decreases) as the negative charge on O bond in CO decreases (because bond order decreases) as the negative charge on

the complexes increases. the complexes increases.

Thus order of CO bond strengths ; Thus order of CO bond strengths ; (a) [M(CO)

(a) [M(CO)₆₆]]++ > [Cr(CO) > [Cr(CO)₆₆] > [V(CO)] > [V(CO)₆₆]] – –_{> [Ti(CO)}_{> [Ti(CO)}

6

6]]22 – –.. ((bb) [) [NNii((CCOO))44] > [Co(CO)] > [Co(CO)44]] – – > [Fe(CO) > [Fe(CO)44]]22 – –..

ETOOS

(14)

PART - I : OBJECTIVE QUESTIONS

**

Marked Questions are having more than one correct option.Marked Questions are having more than one correct option.

SECTION (A) :

INTRODUCTION OF COORDINATION COMPOUNDS

A-1.

A-1. Some salts although containing two different mSome salts although containing two different metallic elements give test for one of them in solution. Such salts are :etallic elements give test for one of them in solution. Such salts are : ((AA) ) ccoommpplleex x ssaalltt ((BB) ) ddoouubblle e ssaalltt ((CC) ) nnoorrmmaal l ssaalltt ((DD) ) nnoonnee

A-2.

A-2. All ligands are :All ligands are :

((AA) ) LLeewwiis s aacciiddss ((BB) ) LLeewwiis s bbaasseess ((CC) ) nneeuuttrraall ((DD) ) nnoonnee A-3.

A-3. Diethylenetriamine is :Diethylenetriamine is :

((AA) ) cchheellaattiinng g aaggeenntt ((BB) ) ttrriiddeennttaatte e nneeuuttrraal l mmoolleeccuullee ((CC) ) ttrriiddeennttaatteemmoonnooaanniioonn ((DD) ) ((AA) ) aannd d ((BB) ) bbootthh

A-4.

A-4. In brown ring complex compond [Fe(HIn brown ring complex compond [Fe(H₂₂O)O)₅₅NO]SONO]SO₄₄, the oxidation state of Fe is :, the oxidation state of Fe is : ((AA)) ++22 ((BB)) ++33 ((CC)) ++44 ((DD)) + 1+ 1 A-5.

A-5. In the complex [CoClIn the complex [CoCl₂₂(en)(en)₂₂]Br, the co-ordination number and oxidation state of cobalt are :]Br, the co-ordination number and oxidation state of cobalt are : ((AA) ) 6 6 aannd d ++33 ((BB) ) 3 3 aannd d ++33 ((CC) ) 4 4 aannd d ++22 ((DD) ) 6 6 aannd d ++11 A-6.

A-6. What is What is the charge on the complex [Cr(Cthe charge on the complex [Cr(C₂₂OO₄₄))₂₂(H(H₂₂O)O)₂₂] formed by Cr(] formed by Cr(!!!!!!) ) ??

((AA))++33 ((BB))++11 ((CC))++22 ((DD)) – –11 A-7.

A-7. Which of Which of the following are bidentate monoanion liganthe following are bidentate monoanion ligands ?ds ?

((11) ) AAcceettyyllaacceettoonnaattoo ((22) ) OOxxaallaatto o iioonn ((33) ) DDiimmeetthhyyllggllyyooxxiimmaattoo Select the correct answer using the

Select the correct answer using the codes given below :codes given below :

((AA) ) 1 1 oonnllyy ((BB) ) 1 1 aannd d 3 3 oonnllyy ((CC) ) 3 3 oonnllyy ((DD) ) 2 2 aannd d 3 3 oonnllyy A-8.

A-8. Match the fMatch the followingollowing

Column-Column- Column- Column-((aa))eenn ((pp)) ((bb))ddmmgg ((qq)) ((cc))EEDDTTAA ((rr)) (d) gly (d) gly ((ee))ooxx ((ss)) (t) (t)

((aa) ) ((bb) ) ((cc) ) ((dd) ) ((ee)) ((aa) ) ((bb) ) ((cc) ) ((dd) ) ((ee)) ((AA)) rr pp tt qq ss ((BB)) rr pp tt qq ss ((CC)) pp ss qq rr tt ((DD)) ss qq tt pp rr

ETOOS

(15)

Page No. # 14 Page No. # 14 A-9.

A-9. The donor sites of (EDTA)The donor sites of (EDTA)44 – –_{are ?}_{are ?}

((AA) ) O O aattoomms s oonnllyy ((BB) ) N N aattoomms s oonnllyy

((CC) ) TTwwo o N N aattoomms s aannd d ffoouur r O O aattoommss ((DD) ) TThhrreee e N N aattoomms s aannd d tthhrreee e O O aattoommss

SECTION (B) :

IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS

B-1.

B-1. The IUPAC name of [CoCl(NOThe IUPAC name of [CoCl(NO₂₂)(en))(en)₂₂] Cl is] Cl is – –

(A) C

(A) Chloridonitrito-hloridonitrito-O-bis(ethylenO-bis(ethylene de diammine)coiammine)cobalt balt (III) (III) chlchlorioridede (B)

(B) Chloridonitrito-Chloridonitrito- N-bis(ethyleN-bis(ethylene ne diammine)cobdiammine)cobalt alt (II) (II) chlchlorioridede (C) Chloridobis(ethane-1,2-diamine)nitrito-N-cobalt(III) chloride (C) Chloridobis(ethane-1,2-diamine)nitrito-N-cobalt(III) chloride (D)

(D) Bis(ethylene diammine)Bis(ethylene diammine) chloridonitrito-N-cobalt(III)chloridonitrito-N-cobalt(III) chloridechloride B-2.

B-2. IUPAC name of [Pt(NHIUPAC name of [Pt(NH₃₃))₃₃(Br)(NO(Br)(NO₂₂)Cl]Cl is)Cl]Cl is – –

(A) Triamminechloridobromonitrito-N-platinum (IV) chloride (A) Triamminechloridobromonitrito-N-platinum (IV) chloride (B)

(B) Triamminebromonitrito-N-chloridoplatinum (IV) Triamminebromonitrito-N-chloridoplatinum (IV) chloridechloride (C)

(C) TriamminebromidochloridonTriamminebromidochloridonitrito-N-platitrito-N-platinum(IV) inum(IV) chloridechloride (D)

(D) Triamminenitrito-N-chloridobromidoplatiTriamminenitrito-N-chloridobromidoplatinum num (IV)(IV) chloridechloride B-3.

B-3. The IUPAC name for [Co(NCS)(NHThe IUPAC name for [Co(NCS)(NH₃₃))₅₅]Cl]Cl₂₂ is is – –

(A) Pentaamminethiocyanato-N-cobalt(III) chloride (A) Pentaamminethiocyanato-N-cobalt(III) chloride (B) Pentaamminethiocyanato-S-cobalt(III) chloride (B) Pentaamminethiocyanato-S-cobalt(III) chloride (C) Pentaamineisothiocyanato-N,S-cobalt(III) chloride (C) Pentaamineisothiocyanato-N,S-cobalt(III) chloride (D) P

(D) Pentaammine (mercapto-N) cobalt(III) entaammine (mercapto-N) cobalt(III) chloridechloride B-4.

B-4. The correct IUPAC name of the complex The correct IUPAC name of the complex Fe(CFe(C₅₅HH₅₅))₂₂ is is – –

((AA) ) CCyyccllooppeennttaaddiieennyylliirroonn((IIII)) ((BB) ) BBiiss((ccyyccllooppeennttaaddiieennyyll))iirroonn((IIII)) ((CC) ) DDiiccyyccllooppeennttaaddiieennyyllffeerrrraattee((IIII)) ((DD)) FerroceneFerrocene

B-5.

B-5. The formula The formula of the of the complex tris(ethane-1complex tris(ethane-1,2- diamine)cobalt(I,2- diamine)cobalt(III) sulphate isII) sulphate is – –

(A) [Co(en)

(A) [Co(en)₂₂SOSO₄₄]] ((BB) ) [[CCoo((eenn))₃₃SOSO₄₄]] ((CC) ) [[CCoo((eenn))₃₃]SO]SO₄₄ (D)(D) [Co(en)[Co(en)₃₃]]₂₂(SO(SO₄₄))₃₃ B-6.

B-6. The IUPAThe IUPAC name C name of Fe(CO)of Fe(CO)₅₅ is is – –

((AA) ) PPeennttaaccaarrbboonnyyllffeerrrraatte e ((00)) ((BB) ) PPeennttaaccaarrbboonnyyllffeerrrraattee((IIIIII)) ((CC) ) PPeennttaaccaarrbboonnyylliirroon n ((00)) ((DD)) Pentacarbonyliron(II)Pentacarbonyliron(II) B-7.

B-7. KK₃₃[Fe(CN)[Fe(CN)₆₆] is] is – –

((aa) P) Poottaassssiiuum hm heexxaaccyynnooffeerrrroouuss((IIIIII)) ((bb) P) Poottaassssiiuum hm heexxaaccyynnooffeerrrraattee((IIIIII)) ((cc) ) PPoottaassssiiuum m ffeerrrriiccyyaanniiddee ((dd)) Hexacyano ferrate(III) potassiumHexacyano ferrate(III) potassium Correct answer is

Correct answer is – –

((AA) ) OOnnlly y ((aa) a) annd d ((bb)) ((BB) O) Onnlly y ((bb) a) annd (d (cc)) ((CC) ) OOnnlly y ((aa) ) aannd d ((cc)) ((DD) ) OOnnlly y ((bb) ) aannd d ((dd)) B-8.

B-8. The IUPAC The IUPAC name of the complex [CrCname of the complex [CrCll₂₂(H(H₂₂O)O)₄₄]NO]NO₃₃isis – –

(A)

(A) DicDichlohloridridoteotetratraaquaquachachromromium(ium(IIIII) nI) nititratratee (B) (B) TTetretraaqaaquaduadichichloloridridochochromiromium(Ium(III) II) ninitratratete ((CC) ) CChhrroommiiuummtteettrraaaaqquuaaddiicchhlloorriiddoonniittrraattee ((DD)) DichloridotetDichloridotetraaquachromium(II) raaquachromium(II) nitratenitrate B-9.

B-9. The chloro-bis (ethylenediaminThe chloro-bis (ethylenediamine) nitro cobalt(III) ion e) nitro cobalt(III) ion isis – –

(A) [Co(NO

(A) [Co(NO₂₂))₂₂(en)(en)₂₂ClCl₂₂]]++ _(B)_{(B) [CoCl(NO}_[CoCl(NO 2

2))22(en)(en)22]]++ (C) (C) [Co(NO[Co(NO22)Cl(en))Cl(en)22]]++ (D)(D) [Co(en)Cl[Co(en)Cl22(NO(NO22))22]] – – B-10.

B-10. A complex anion is formed by Osmium (in some oxidation state) with ligands (in proper number so that coordinationA complex anion is formed by Osmium (in some oxidation state) with ligands (in proper number so that coordination number of osmium

number of osmium becomes six). Wbecomes six). W hich of the following can be its correct IUPAhich of the following can be its correct IUPAC name?C name? ((AA) p) peennttaacchhlloorriiddoonniittrriiddoooossmmiiuumm((VVII)) ((BB) p) peennttaacchhlloorriiddoonniittrriiddoooossmmaattee((VVII)) ((CC) ) aazziiddooppeennttaacchhlloorriiddoooossmmaattee((VVII)) ((DD) ) NNoonne e oof f tthheessee

ETOOS

IIT JEE Coordination Compound Etoos DPP

Contents

Contents

Syllabus

Syllabus

Name : _

Name : _________________

___________________________ Contact No. _______

___________ Contact No. _________________

___________

_

ETOOS

ETOOS

INDIA.COM

INDIA.COM

India's No.1 Online Coaching for JEE Main & Advanced

India's No.1 Online Coaching for JEE Main & Advanced

3rd Floor, H.No.50 Rajeev Gandhi Nagar, Kota, Rajasthan 324005

3rd Floor, H.No.50 Rajeev Gandhi Nagar, Kota, Rajasthan 324005

HelpDesk : Tel. 092142 33303

HelpDesk : Tel. 092142 33303

Coordination Compound

Coordination Compound

IIT JEE 201

IIT JEE 201

COORDINA

COORDINATION

TION COMPOUNDS

COMPOUNDS

Coordination Compounds :

Coordination Compounds :

Various Terms Used in co ordination compounds :

Various Terms Used in co ordination compounds :

Central Atom/Ion :

Central Atom/Ion :

Ligands :

Ligands :

Coordination Number :

Coordination Number :

Nomenclature of Coordination Compounds

Nomenclature of Coordination Compounds

BONDING IN COORDINATION COMPOUNDS :

BONDING IN COORDINATION COMPOUNDS :

Werner's Theory :

Werner's Theory :

Effective Atomic Number Rule given by Sidgwick :

Effective Atomic Number Rule given by Sidgwick :

Valence bond theory :

Valence bond theory :

Crystal Field Theory :

Crystal Field Theory :

COLOUR IN COORDINATION COMPOUNDS :

COLOUR IN COORDINATION COMPOUNDS :

ISOMERISM :

ISOMERISM :

STRUCTURAL ISOMERISM :

STRUCTURAL ISOMERISM :

Stereoisomerism

Stereoisomerism

Geometrical Isomerism

Geometrical Isomerism

Optical Isomerism :

Optical Isomerism :

Organometallic compounds :

Organometallic compounds :

Bonding in Metal Carbonyls

Bonding in Metal Carbonyls

PART - I : OBJECTIVE QUESTIONS

PART - I : OBJECTIVE QUESTIONS

**

SECTION (A) :

SECTION (A) :

INTRODUCTION OF COORDINATION COMPOUNDS

INTRODUCTION OF COORDINATION COMPOUNDS

SECTION (B) :

SECTION (B) :

IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS

IUPAC NOMENCLATURE OF COORDINATION COMPOUNDS

_____________________ Contact No. _

_ Contact No. _______