By C.H. Bamford and C.F.H. Tipper (Eds.)
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Extra resources for Reactions of Metallic Salts and Complexes, and Organometallic Compounds
2 lo-’ ~ 5 . 8 x 10-3 1 . 6 lo-’ ~ ReJ 81 81 81 81 90 90 90 6. Complexes with B class ligands: the binary carbonyls The characteristic of these complexes in general is that ligands very often possess vacant (x-bonding) orbitals. It applies particularly to those unsaturated ligands, such as CN, CO and hydrocarbons with relatively low energy (and vacant) antibonding orbitals, less particularly to the ligand atoms with relatively low energy (and vacant) d orbitals (those which do not belong to the first short period).
Fortunately, there is an alternative account of the situation. The dissociative transition state is an incipient five coordinate complex. In the extreme case there are two possible geometries, trigonal bipyramidal and square pyramidal and different ligands may stabilize geometrically different transition states. Note (Fig. 1 cis A Fig. 6 . Stereochemical changes accompanying the dissociative reaction MA4BX + MA4B + MA4BY. whereas the trigonal bipyramidal form can. A fairly satisfactory correlation between stereochemical rearrangement emerges following the suggestion” that the formation of a strongly trigonal form is accompanied by a positive AS’.
T A B L E I2 (1. 6 at 25 "C; at 22 "C. 1 M ) * Data from ref. References p p . 52-55 170. AT F e ( C O ) 2 ( N O ) zA N D 25 "C. 5 Y l o y 6 sec-' sec-' 34 I N E R T COMPLEXES A N D M E T A L O R G A N I C C O M P O U N D S In the case of the nickel compounds, further substitution which is first-order takes placelZ0 Ni(CO),LL‘+CO (27) +L’ + Ni(CO),LL’ + L (28) Ni(CO),L+L’ -+ or Ni(CO),L, While the rate is independent of both the concentration and the nature of L’, it varies with L as: L = Cl,P > (C6H5),P > (n-But),P > (C,H,O),P > > (C6H,0),P.
Reactions of Metallic Salts and Complexes, and Organometallic Compounds by C.H. Bamford and C.F.H. Tipper (Eds.)