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Coordination chem of d .

f block main group


Advanced Inorganic Chem Chem 112 UP Diliman prepared by Eva Ratilla

Review concepts
d block vs transition elements
d e vs incomplete d shell Electronic configurations Triad Platinum group

Physical properties
Hard, malleable, ductile, electrical conductor Metallic size s block vs d-block cn 12 cp Lanthanide contraction bet 4d and 5d approx same size in a row for d block S size > d size Harder d than s block Less volatile than s block

S vs d block metals and metallic radii

Mn atypical cubic w 4 sites of different CN

atomization enthalpy

Characteristic properties and reactivities


Formation of ions ' f G = -nFEox = nFEred = ' f H T' f S = - >'aG + 'hydG + ~( IE1+IE2)] 'G1 Fe2+ (aq) + 2e Fe(s) 'hydG
IE1+IE2 Fe2+(g) + 2e Fe(g)

'aG

d9 s2 d9 vs d9 s2 d10

d4 s2 d4 vs d4 s2 d5

E0 M+2/M Also reflects d e distribution, IE1 + IE2 Irving Williams series

General reactivities
Binary oxide, sulfide, halide formation When heated in O2 M2On in S M2Sn in X2 MXn Interstitial hydrides may form with H2 also borides, carbides, nitrides Most M in acids H2 (corrode) But passivation or oxide formation prevents some

M+2 + 2Cl- MCl2 M + Cl2

Colors or Spectra
Most colored Absence of color no dd or very high energy uv or low energy ir Intensity of color depends if allowed orbitally and by spin conservation rules Color transmitted complementary to color absorbed Aq ions due to d-d transitions
Oh wea k band pale due to La Porte forbidden gg but when no Inversion center in complex like Td strong

But ionized coordinated water produces intense color due to charge transfer from ligand oxide or hydroxide to metal d orbitals or LMCT In other complexes intense colors due to MLCT or with S rich ligand based transitions

Magnetic Properties
Usually on account of unpaired d e Paramagnetic species Diamagnetic e all paired Magnetic moments, P, and susceptibilities Fm measured P spin only = n(n+2) = 2 S(S+1) Also detecred with EPR and Mossbauer Manifest in NMR with anomalous chemical shifts and shapes in lines, relaxation lifetimes in MRI as relaxation agents

Complex Formation
Kf = Kins -1 'fG = -RT ln Kf For aq ions (Oh) weak ligand field follow Irving-William Series Assocd w d e distribution and LFSE ligand field stabilization energies

Cu2+ d9 Oh undergo Jahn Teller distortion remove degeneracy or H2O

E 6 = K1K2K3K4K5K6 or overall constant

d orbitals

Keppert Model
Vs VSEPR d block M is a sphere Ligands free to move around M sphere surface Ignores non bonding e AXn Minimize ligand repulsions Not usually followed in alternative geometries

CN3 trigonal planar uncommon CN 2 linear uncommon [AgTe7]3Fe[N(SiMe3)2]3 + Au[P-cyclo-C6H11)3]2

Usually d10 CuI , AgI, AuI. HgII also Pt(0) in CN3 and bulky amido N(SiMe3)2]- forces low CN

Werners Valence Band Approach Metal ion forms hybrid orbitals for V bonds
d10 d10 d6 d8 d9 d8 d6 d0 d0 d0 d0 d0 d0 d0

dsp2 dsp3 d2sp3\ d5s


Or

d2sp3 d3sp3 d3sp3

fd3sp3 d4sp3 d4sp3 d5sp3

CN4 Td vs Sq Pl, D4h


Td is common except no d3 yet d4 needs to be stabilized by bulky amido ligands like M(NPh2)4 and M[N(SiMe3)2]3Cl for Hf and Zr sp3 hybrid d8 favors sq planar dsp2 hybrid from dx2-y2, s, px,py

CN4 sq pl rare often w d8 Distorted Rh(PMe2Ph)4]+

Zn(N(EtNH2)3)Cl]+

[Cu bpy (NH(CH2COO)2)]

CN5 Tbp vs Sq Pyramid


Small energy differences
Tbp d10 CdCl5]3-, HgCl5]3-, CuCl5]3 sp3d with dz2 Sq py in oxo or nitrido complexes of d0 Nb, d1 V , W, and Tc, d2 Tc and Re sp3d with dx2- y2

Tripodal ligands favor CN 5 tbp

CN 6 Oh and Trig Psm D3h


Oh common for d0 to d10 d2sp3 strong and low spin and sp3d2 weak hi spin using dz2 and dx2-y2 d4 and d9 tetragonal distortion, removes degeneracy, Jahn Teller effect d0 and d1 Trig prismatic D3h with V donor ligands not S donor nor S acceptor Like MoMe6, WMe6, NbMe6]- , TaMe6] d5s or d2sp3 with dxz and dyz