Metal cluster alkoxide ligands

A rare example of the formation of an alkoxide ligand in a metal cluster compound is seen in the reaction between methyl fluorosulfonate and the triiron carbonyl clusters anion [Fe3(CO)9(/i3-MeCO)], which gives Fe3(CO)9(/x3-CMe)(/i3-OMe) by C—O bond cleavage.135,136 The C—O bond cleavage provides a possible model for a step in Fischer-Tropsch chemistry.121... 

M. H. Chisholm, Ed., Early Transition Metal Clusters with n-Donor Ligands, VCH Publishers, New York, 1995 (polyoxo and alkoxide clusters). 

Metal oxo-alkoxides, MO (OR)x 2 > , may be considered intermediates between metal alkoxides M(OR)x and the corresponding metal oxide, and are the counterparts of the polyanions and polycations in aqueous systems. Controlled partial hydrolysis of M(OR)x (Equation (20)) does indeed sometimes result in structurally well-defined metal oxo-alkoxo oligomers (clusters) where //2—0x0 ligands connect the metal polyhedrons from which the clusters are constructed. 

II. Early Transition Metal Clusters with Halide and Alkoxide Ligands... 

III. EARLY TRANSITION METAL CLUSTERS WITH HALIDE AND ALKOXIDE LIGANDS... 

See also Chapter 4. The molybdenum (II) alkoxides isolated as alcohol or amine solvates of [Mo(OR)2L2] composition are the typical examples of binu-clear clusters with a quadruple metal-metal bond not supported by any bridging ligands. Square planar coordinated (not taking into account the M-M bond) metal atoms are situated exactly in front of each other, which leads to the molecules with eclipsed conformation. 

---