Bromination of Molybdenum Carbonyls Revisited: Oxo Complexes and Routes to New Materials Chemistry
The use of in situ [MoBr(μ-Br)(CO)42] led to considerably improved preparations of [MoBr2(CO)3(PPh3)2] for which the rate of decarbonylation to [MoBr2(CO)2(PPh3)2] is greatly increased by refluxing under reduced pressure (15-20 mmHg). Attempts to prepare [MoBr2(CO)2P(C6H11) 32] by Br2 addition to cis- or trans-[Mo(CO)4P(C6H11)3 2] led to [HP(C6H11)3][Mo(=O)Br4L] [L = OP(C6H11)3 or H2O]. The OP(C6H11)3 complex may be used as a catalyst for the epoxidation of cyclohexene or for the addition of singlet oxygen to α-terpinene (1-isopropyl-4-methylcyclohexa-1,3-diene). The species [HP(C6H11)3][Mo(=O)Br4OP(C 6H11)3] was adsorbed onto sodium montmorillonite in a new type of reaction for sodium montmorillonite involving multiple abstractions of NaBr from the complex anion. In solution [HP(C6H11)3][Mo(=O)Br4OP(C 6H11)3] also decomposes to crystalline [Mo(=O)2Br2OP(C6H11) 32] which is monoclinic, space group C2/c [a = 27.15(5), b = 8.486(8), c = 18.49(2) Å, β = 110.94(7)°].
J. R. Backhouse et al., "Bromination of Molybdenum Carbonyls Revisited: Oxo Complexes and Routes to New Materials Chemistry," Journal of the Chemical Society, Dalton Transactions, Royal Society of Chemistry, Jan 1995.
The definitive version is available at https://doi.org/10.1039/DT9950001489
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