Toward cationic gallane- and indanediyl complexes: synthetic approaches to three-coordinate halogallyl and -indyl precursors

Bunn, Natalie R., Aldridge, Simon, Kays (née Coombs), Deborah L., Coombs, Natalie D., Day, Joanna K., Ooi, Li-ling, Coles, Simon J. and Hursthouse, Michael B. (2005) Toward cationic gallane- and indanediyl complexes: synthetic approaches to three-coordinate halogallyl and -indyl precursors. Organometallics, 24 (24), 5879-5890. (doi:10.1021/om050630f).

Abstract

Transition metal complexes containing ligands featuring three-coordinate, halide-functionalized gallium or indium donors represent key precursors to unsaturated cationic species of the type [LnM(EX)]+ via halide abstraction chemistry. Two routes to these three-coordinate systems have been demonstrated: (i) salt elimination, such as the reaction between Na[Cp*Fe(CO)2] and Mes*GaCl2 or Mes*InBr2 (Mes* = C6H2tBu3-2,4,6, supermesityl) to generate Cp*Fe(CO)2E(Mes*)X (3a, E = Ga, X = Cl; 5, E = In, X = Br), and (ii) insertion of a gallium(I) or indium(I) halide into a metal-halogen or metal-metal bond followed, where necessary, by substitution by a sterically bulky anionic nucleophile. Crystallographic studies have confirmed the presence of the target trigonal planar ligand systems both in gallyl/indyl complexes of the type LnM-E(Aryl)X and in halide-functionalized gallane- and indane-diyl systems of the type (LnM)2EX.

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Contributors

Author: Simon J. Coles

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