Chapter 18. (Bonding in Transition Metals and Coordination Complexes) : d. (unpaired electrons). LUMO.., 18.1 4 (d Sc Zn).. ( 18.1 ) IE1 IE2 :..
2+ 2+ M ( g) M ( aq). 2 2 M + ( g) + 6 HOl ( ) [ M( HO) ] + 2 2 6 -
18.2 (II), CuSO 5H O [ CuHO ( ) ] SO HO 4 2 2 4 4 2 (II) 4 HO 2 (ligand) (II) (coordination sphere). [ CuHO ( ) ] SO HO HO. 2 4 4 2 2 - (2 6) (coordination number). (monodentate) : 1. (F -, Cl -, Br -, I - ), (NH ), CO, H 2 O (bidentate) : (ethylenediamine, NH 2 CH 2 CH 2 NH 2 ) Co + 6(=*2) [Co(en) ] +. (chelate). [Pt(NH ) 6 ]Cl 4 Pt 6 NH.. 18.1 10.. Mn CO, 2 10 [Re Br12], + [ Fe( H O)( OH )], 2 4 2 [ Co( NH ) Cl ] 4 2 +
.. [ Pt( NH ) ] [ PtCl ] 2+ 2 4 4 [ Pt( NH) 4][ PtCl 4]. [ Pt( NH ] ) 4][ PtCl 4 [ Pt( NH) 2Cl2] [ Pt( NH) Cl][ Pt( NH) Cl] [ Pt( NH) Cl] 2[ PtCl4] [ Pt( NH) 4][ Pt( NH) Cl] 2 Pt : NH : Cl = 1 : 2 : 2... 18.2 12.. (a) Silver hexacyanoferrate(ii) (b) potassium tetraisothiocyanatocobaltate(ii) (c) sodium hexafluorovanadate(iii) (d) potassium trioxalatochromate(iii)
NiSO () s + 6 H O( g) [ Ni( H O)] SO () s 4 2 2 6 4 NiSO () s + 6 NH ( g) [ Ni( NH )] SO () s 4 6-2 2 [ Ni( H O) ] + + 6 NH ( aq) [ Ni( NH ) ] + + 6 H O( aq) 2 6 6 2 - (labile) (inert). 4 18. 19 (Alfred Werner) [ Co( NH ) ] + 6 [ Co( NH ) ] + 2+ [ Co( NH ) Cl]. 6 [ Co( NH ) ] + + [ Co( NH ) Cl ]. 6 5 4 2 (geometrical isomer) : (cis) (trans)
[ CoCl ( en) ]. + 2 2 [ Co( NH ) Cl ] 4+ [ Pt( en) ] (enantiomer).
[ Co( NH) 2( H 2O) 2Cl2] + 2, 2, 2? [ Pt( NH ) Cl F ] 2 2 2,.
EDTA(ethylenediaminetetraacetate ). Pt(II) Pt(IV)? Ni(II),??
(crystal field stabilization energy, CFSE):
(diamagnetic):. (magnetic susceptibility).. (paramagnetic):.. (unpaired electron). 18.5 27.. [ Fe( CN) ] [ Fe( H O ) ] +. 2 6?. 6 0.
18.5. + [ Co( NH ) ] 6 [ Co( NH ) Cl ] + 4 2 Co NH 5H2O + [ ( ) ] ( ) :.. 2 [ Co( NH ) Cl] + ( ) 5-50 nm.. hν = 0 (. ν ) ( λ = c/ h) ) ( 0
(spectrochemical series): ( 0 ) I < Br < Cl < F, OH < H O< : NCS < NH < en< CO, CN 2 ( ) ( ) 18.6. [ FeF ], [ Fe( CN) ], [ Fe( H O) ] + 6 6 2 6 :. NH CO F -. (ligand field theory):. d, s p - 6.
I -, Br -, Cl -, F - p y d xy t 2g. 0. CO CN - π- (π back bonding) t 2g 0. H 2 O NH -. 18.6 (organometallic compound):. 60 o C Ni() s + 4 CO( g) Ni( CO)( g) 4 4 200 o C Ni( CO) ( g) Ni( s) + 4 CO( g) Fe( CO ) 5 : (trigonal bipyramidal) Mn ( CO ) 2 10 Co ( CO ) 2 8 VCO ( ) 6 : 18-electron rule Sandwich compound 2 Fe( C H ) (ferrocene): Fe + 2 CH 5 5 5 5 2 (cyclopentadienyl).
- : Porphine:,, B 12