Halide bridged complexes reactions

The chromium(II) reductions of a number of trans-dihalide ruthenium (III) complexes are inner sphere in nature with halide bridging groups. Reaction rates are sensitive to steric effects, whereas the corresponding reductions by vanadium(II) show little steric variation, exceed the V " ligand substitution rate, and must be considered outer sphere. 

The cyclometallated acetophenone oxime complex [PdCl C6H4C(Me)N-(0H) ]2 undergoes halide bridge splitting reactions with electron-rich olefins (8) to afford the carbene derivatives (70). The use of diazoalkanes as carbene ligand precursors has been reviewed. ... 

Subtle changes may influence the outcome of such reactions. Thus, the formation of a binuclear, halide bridged Fe-Cd complex was observed exclusively when starting from CdBr2 whereas only trinuclear Fe-Cd-Fe chains where found in the case of CdCl2 13c, d]. 

In the reaction of group 13 element halides with metal carbonyl dianions, the analysis is more complex than observed for the reactions with metal monoanions. Upon addition of metal dianions to EX3 or REX3, either one or two halide ions may be eliminated. When only one halide ion is eliminated per added metal dianion, the complexes may still be viewed as E3+ derivatives (Equations (33)-(36)).19 This may be controlled to some extent by the stoichiometry of the reaction. Comparison of Equations (33)19 and (34)19 shows that the electron demand at the main group element can be satisfied by coordination either to an electron-rich metal center 26 or formation of a halide bridge 27. Ligand-stabilized forms may also be prepared in this fashion (Equation (36)).19... 

---