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    Coordination Compd Tricks PDF

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    Youtuber RS

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    © All Rights Reserved
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    Trick 6 Tech: Double salts when dissolved in water dissociate almost completely into ions in the same way in which the individual components of the double salts do, It means in aqucous solution, they give the test of all their constituent ions. In complex compounds, the central metal atom or ion can act as Lewis acid and ligands act as Lewis base. In complex compounds central metal may exists in zero, positive or even in low negative oxidation state. Chelating ligand is a natural molecule, free radical or ion with two or more lone pairs of electrons on different atoms, formation of chelate rings always increases the stability of a complex. r-acid ligand are capable of accepting an appreciable amount of x-electron density from the metal atom into empty 1 or x* orbital of their own. TUPAC nomenclature of complex compounds @ The positive part of a coordination compound is named first and is followed by the name of negative part @ The ligands are named first followed by the central metal. The prefixes di-, tri etc, are also used to indicate number of each kind of ligand present. @ The oxidation state of central metal is indicated in roman numbers in parantheses @ Ifa complex species has negative charge, the name of the central metal ends in cate. ®@ If complex is neutral or positive charge than general name is there. Isomerism @ _ Ionisation isomerism arises when complex compounds with same molecular formula give different ions in solution. @ Linkage isomerism arises when a complex contain a monodentate ligand with more than one donor atoms. ®@ Coordination isomerism arises when there is exchange of ligands between complex cation and complex anion, @ Hydrate isomerism arises when different number of water molecules present in the coordination sphere @ Geometrical isomerism arises when two identical ligands oct positions to each other or placed opposite to each other. @ Square planar complexes of the type MA2X)MABX,,MA,XY and MABXY and octahedral complexes of the type MA4X2,MAgX. show geometrical isomerism. py adjacent Bos Rue Trick & Tech: The complex of the type M(AA), Xp (where, AA is symmetrical bidentate ligand) also show geometrical isomerism. @ — Compounds of type MAX 2Y>,MA,XYZ,MA,X,YZL, MABXZL,M(AA);,M(AA)X_» show optical @ MAX, show both geometrical and optical isomerism. isomerism, 7. Primary valencies corresponds to the oxidation number of metal atom or ion while secondary valencies corresponds to the coordination number of metal atom or metal ion, Primary valencies are ionizable while secondary valencies are non ionisable. 8. According to valence bond theory, the metal atom or ion under the influence of ligands can use (n—1) d, ns, np, nd orbitals for hybridisation to yield square planar. tetrahedral or octahedral geometry. These hybridised orbitals then overlap with ligand orbitals which can donate an electron pair for bonding. 9. The crystal field theory is based on the effect of different crystal fields provided by the ligands on the degeneracy of d-orbitals of central metal atom or ion. The conversion of, degenerate d-orbitals into different sets of orbitals having different energies is known as crystal field splitting, © Order of increasing field strength of ligands is as follows I
    is paramagnetic while [Ni(CN4)}> is diamagnetic. It is due to the fact that Clis a weak field ligand, it cannot pair up 3d-electrons against Hund’s rule and Ni?" is sp? Hybridised (tetrahedral shape) with two unpaired electrons. While CN~ is a strong field ligand, causes pairing so, Ni2* becomes dsp” hybridised (square planar shape) with no unpaired electrons (diamagnetic) 13. Structure of[Cu(NHs), * is an exceptional case. In this complex, one electron from, 3d-subshell is promoted to 4p-subshell. The remaining eight 3d-electrons pairs up in four 3d-orbitals followed by spd hybridisation. The resulting complex is square planar with one unpaired clectron in 4p-orbital. It is therefore, paramagnetic. hl one or more unpaired electrons are 14. 1S. 16. 17. 18. 19. 20. Trick 6 Tech: fi Pt (Il) and Au (III) always form square planar complexes whether ligands are strong or weak. (important) All octahedral complexes of Ni?*,Cu*, Zn?* and Co”* are outer orbital complexes. Some complexes likes CrO} ,Cr,0",MnOj ete. have d° configuration of metal ion but have intense colour. In these cases, the colour is due to charge transfer and not due to d —d transition. In organometallic compounds, carbon must be bonded to metal directly. Zeise’s salt, ferrocene and dibenzene chromium are some of the examples of -complex organometallic compounds. complex. Metal carbonyls such as Fe(CO), |,[ Ni(CO), |have characteristics of both o and x complexes. Carbonyls containing metal and Co only are known as homoleptic carbonyls. d-block metals form most stable carbonyls. ‘The stability of coordination compounds is measured in terms of stepwise stability (or formation) constant K or overall stability constant (B). For a given reaction; M+4L— ML, p, - Meal iMiiLy The instability constant or the dissociation constant of coordination compounds is defined as the reciprocal of the formation constant. About the coordinate compound: [ouble salt is that which has wo salts erystalised. in a formula and gives individual identity of the constituents ions. methyl aluminium is an example of o-bonded Example:- Alum is a double salt K,SO,Alo(SO,)3 24 H,0 Gives, K',SO,—AI'™*, SO, But in case of complex compound or Coordinate Compounds we have a Complicated part or ion which is not further dissociated. Example K,[Fe (CN)s]—> 4K* + [Fe (CN)g- ~~ 4 CN” (CN“ testis not given by the complex) [Fe (CN),]-~~~ can not be further dissociated and known as complex or coordinate ion. Coordinate Compounds have four main parts. Ke (fe, (CN)g] Coste ental “Ligand & 7 ene Trick & Tech: Box [Fe(CN).] know as coordinate sphere or complex sphere. @ For complex formation central metal should have high charge and small size. ®@ — Central metal is bonded with coordinate bond and each central metal has fixed number of coordinate bond this number is known as coordination number. (C.N.), Metal GN. (Coordination number) Ag 2 Fe 6 oS Cu 4 re 6 Ni 4 @ — Means K,[FeCl,]is not possible because in this Fe is having ‘4’ coordinate bond or ‘4’ coordination number but for ‘Fe’ Coordination number is '6. K,[AgCls] is wrong because Ag having C. K,[NiCI,] is wrong because Ni having C.) 21. Complexes are of three types. (a) Anionic (b) Cationic (c) Neutral (a) Anionic: In case of Anionic complex coordinate sphere is having negative charge Example: K,[Fe (CN)]—> 4K* + [Fe (CN)g]™ Negativly charge (Coordination sphere) (b) Cationic: In case of cationic complex coordinate sphere positive charge Example: [Fe (H,0),]S0, —>[Fe(H,0)_]"= SOz7 Posty cherged (ce) Neutral: In case of neutral there is no charge on the sphere, Example: Fe(CO); or Ni(CO), 22. For the Stability of Complex: we have thse points. (a) If in complexes central metals are same with same legend then more the charge on. central metal more will be stability. Example: (a) K,[Fe(CN)5] and (b) KglFe(CN)g} In (a) central metal charge is +2 and in (b) charge on central metal is +3, So more Charge is in *b’. so more stable is (b) [This charge is oxidation number] os Trick 6 Tech: K4[Fe(CN)g] Ks[Fe(CN)<] x4 +x+(-1)x6=0 1x34 X+(-1)x6=0 Xei2 xed (b) If we are having same charge on central metal but different ligand then ligand with better basic nature will have more stable complex. Example: (a) Kq[FeCls] and (b) KglFe(CN)g] In both oxidation number of Fe is +2 but CN~ is more basic then CI So. (b) is more stable. @ = Trick For finding basic nature of ligand find out it's acid. If acid is strong then base will be weak and if acid is weak then base will be strong, Some acidic orders are as. HI> HBr > HCl> HCN > H,0 > NH, So basic nature is I" CN™ >CI” So stability is b > a > c 23, EAN =Atomic number+2xcoordination number(C.N.)—oxidation number. Example: EAN of K,[Fe(CN),] Atomic number of Fe = 26 C.N. of Fe is 6. oxidation number = +2 So EAN = 26+ 2 x 6-2 = 36 Find out type of ligand if it is anionic then word 'O’ or ‘ido’ will be there. For cationic wwe use the word ‘ium’ If ligands is having big group then we use 'bis' for two, 'tries' for three and ‘tetrakis' for four. 24, [In case of structure we have following isomerism. (a) Ionisation Isomerism (b) Hydrate Isomerism (c) Coordinate isomerism (d) Linkage Isomerism (¢) Polymer isomerism (f)_ Coordinate sphere isomerism (a) Tonisation Isomerism: In this (wo isomers are diller duc ( change in ions with same molecular formula. [Fe(H,0),CI]Br it gives Br ion. [Fe(H,0);Br]Cl it gives CI” ion. 99, ene Trick & Tech: (b) Hydrate Isomerism: In this type of Isomerism we are having difference between number of water molecules inside and outside the coordinate sphere or difference in water molecule as ligand. (i) [Fe(H,0),CIJCl,.H,0 (ii) [Fe(H,0),]Cls (©) Coordination Isomerism: When we are having a double complex in which both the cation and anion are complex and we are having Exchange of cation in the spheres then this isomerism arises, [Fe(NHs)6][CrClg] and [Cr(NHg)g][FeClg] in this Fe and Cr are Exchange, (4) Linkage Isomerism: In this isomerism linkage of central metal with ligand is changed and in this ambidentate ligand is used. [Fe(NH5);NO,]* and [Fe(NH3);ONO]** in first link with N and in second link with O. (ec) Polymerisation Isomerism: 1 this isomerism one molecule is polymerised with other to give a chain. 2Ni(NH3)Cl, —{Ni(NH),Cly]X2 ® —Ni(NHq)4Cl, means two molecules became [Ni(NH3)4] [NiCl,] and this repeated again and again. © It is developed due to the different possible geometrical arrangements of the ligand around the central atom, Some points: @ For geometrical isomerism Coordination number should be ‘4’ or ‘6" and the condition should be Mazb,,Mab ¢,, Madbed, Ma, bz but Mazb , Ma,, Masb and Mag it is not possible © For geometrical Isomerism shape should not be tetrahedral. for ‘4’ coordination number shape should be planner. Example: In Ma, b, Ne trans. eP a) Bob Trans. cis ‘Same groups on ‘Same groups on ‘opposite side the same side Example: [Cu Cl; (CN)2]~{Ni (CN)2Brg]~ In case of “6 coordinate number if, May by is there then 100 e Trick 6 Tech: mls ac. 1 Na b Trans cis ‘Same groups on opposite (up and down) Example: [Fe (Co),Cl.] ¢ 3 lore Soe ; “Sco cl > in @ Fac and Mer Isomers re observed in case of May by in this ligands form by the same side arraignments form and when on meridional side they form ‘ Mer’. Example: [Co (CN)3(NHs)3] When all the 'NH,'or ‘CN’ are connected then itis known as ‘Fac! because it form a face. NHg 2 CN 3 SN Itis known as mer Co: (meridional) 0 ene Trick & Tech: 25. Degenerate orbitals: In free state , all the d-orbitals (viz, dy. dy.edeuly » and d_,) have same energy and are said to be degenerate. toe and eg Set of orbitals: In a d-subshell, there are five d-orbitals and on the basis of orientation of lobes of the five d-orbitals with respect to coordinates, these have been grounded into two sets: (i ég set of orbitals: dy. and d_, orbitals have their lobes arranged along the axes and they constitute ¢, set. These orbitals are also named as axial orbitals. Term ¢, refers to double degenerate according to group theory. (e=doubly degenerate set) (ii) ty, set of orbitals: This set includes orbitals whose lobes lie between the axes and this set includes dy,d,, and d,, orbitals. These orbitals are also known as d, or non-axial orbitals. Group theory calls these orbitals as tp, where ‘t’ refers to triply degenerate, 26 egldZ.4,2 2) = 16 Dg CFSE (Dp)=10 Dg, 5 4g” Bari centre G togi(dxy.dyz.chz) “arias, Octahedral Crystal in free ion (M"*) 27 xy dye dhe olin tag 4 Dh 2? de Average eneray \O}% 3 ¥ # | 2 of d-orbitals. a ina symmetrical e ‘c-orbitals crystal field Splitting ina in free ion tetrahedral crystal field 102 28. 29. 30. Trick 6 Tech: > Average energy 4 8 ina symmetical [> 42 & crystal field bs orbitals Spitting in square in free ion Octahedral planar crystal field Nature of Central Metal Atom (a) Size of central metal ion: M?" ions of 3d-series, ‘maller cations form more stable complexes. e.g, for Ionic radii Mn** >Fe® >CO* >Ni# >CU* CU*

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