H. Arzoumanian et al., DIOXYGEN LIGAND TRANSFER FROM PLATINUM TO MOLYBDENUM - ISOLATION OF AHIGHLY REACTIVE MOLYBDENUM(VI) OXOPEROXO DIMER, Bulletin de la Societe chimique de France, 132(11), 1995, pp. 1119-1122
The reaction of Pt(O-2)(PPh(3))(2) with Mo(O)(2)(mesityl)(2) (mesityl
= 2,4,6-Me(3)C(6)H(2)) in pyridine results in the transfer of the diox
ygen ligand from platinum to molybdenum giving, in the presence of PPh
(4)Cl, a molybdenum peroxo compound 1 in which all the organic moietie
s have been lost. This compound epoxidizes tetracyanoethylene at a rat
e estimated at 10(4) greater than the known oxodiperoxomolybdenum comp
lex 2. Furthermore, 1 exhibits a high selectivity for electron-poor ol
efins (TCNE/cyclooctene = 10(3)). Elemental analysis, IR and O-17 NMR
indicate that 1 is the tetraphenylphosphonium salt of an oxoperoxomoly
bdenum(VI) dimer.