Alkoxide Clusters of Molybdenum and Tungsten as Templates for Organometallic Chemistry: Comparison with Carbonyl Clusters of the Later Transition Elements

Abstract Alkoxide and carbonyl ligands complement each other because they both behave as “π buffers” to transition metals. Alkoxides, which are π donors, stabilize early transition metals in high oxidation states by donating electrons into vacant d π orbitals, whereas carbonyls, which are π acceptors, stabilize later transition elements in their lower oxidation states by accepting electrons from filled d π orbitals. Both ligands readily form bridges that span MM bonds. In solution fluxional processes that involve bridge–terminal ligand exchange are common to both alkoxide and carbonyl ligands. The fragments [W(OR) 3 ], [CpW(CO) 2 ], [Co(CO) 3 ], and CH are related by the isolobal analogy. Thus the compounds [(RO) 3 W W(OR) 3 ], [Cp(CO) 2 WW(CO) 2 Cp], hypothetical [(CO) 3 CoCo(CO) 3 ], and HCCH are isolobal. Alkoxide and carbonyl cluster compounds often exhibit striking similarities with respect to substrate binding—e.g., [W 3 (μ 3 ‐CR)(OR′) 9 ] versus [Co 3 (μ 3 ‐CR)(CO) 9 ] and [W 4 (C)(NMe)(O i Pr) 12 ] versus [Fe 4 (C)(CO) 13 ]—but differ with respect to MM bonding. The carbonyl clusters use e g ‐type orbitals for MM bonding whereas the alkoxide clusters employ t 2g ‐type orbitals. Another point of difference involves electronic saturation. In general, each metal atom in a metal carbonyl cluster has an 18‐electron count; thus, activation of the cluster often requires thermal or photochemical CO expulsion or MM bond homolysis. Alkoxide clusters, on the other hand, behave as electronically unsaturated species because the π electrons are ligand‐centered and the LUMO metal‐centered. Also, access to the metal centers may be sterically controlled in metal alkoxide clusters by choice of alkoxide groups whereas ancillary ligands such as tertiary phosphanes or cyclopentadienes must be introduced if steric factors are to be modified in carbonyl clusters. A comparison of the reactivity of alkynes and ethylene with dinuclear alkoxide and carbonyl compounds is presented. For the carbonyl compounds CO ligand loss is a prerequisite for substrate uptake and subsequent activation. For [M 2 (OR) 6 ] compounds (M = Mo and W) the nature of substrate uptake and activation is dependent upon the choice of M and R, leading to a more diverse chemistry.