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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
atomization enthalpy
'aG
d9 s2 d9 vs d9 s2 d10
d4 s2 d4 vs d4 s2 d5
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
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
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
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
Zn(N(EtNH2)3)Cl]+