Formation of organometallic hydroxo and oxo complexes by oxidation of transition metal hydrides in the presence of water. X-Ray structures of [CpMo(OH)(PMe3)3][BF4] and [CpMo(O)(PMe3)2][BF4]

Abstract

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High oxidation state organomolybdenum and organotungsten chemistry in protic environments

“…By analogy with the Cp 2 Mo 2+ system, the presence of soft phosphine donor ligands destabilizes the highest oxidation states, these derivatives existing only in oxidation states up to IV. [113] precursors upon reaction with water. In the latter case, DFT studies and the isolation of intermediates indicates a complex mechanism involving water-induced disproportionation of the paramagnetic (17- [114]), and further oxidation, deprotonation and PMe 3 decoordination to complete the process [113].…”

“…[113] precursors upon reaction with water. In the latter case, DFT studies and the isolation of intermediates indicates a complex mechanism involving water-induced disproportionation of the paramagnetic (17- [114]), and further oxidation, deprotonation and PMe 3 decoordination to complete the process [113]. Oxidation of compounds [(C 5 R 5 )Mo(dppe)H 3 ] (R = Me, Et) in the presence of water, on the other hand, yields the neutral bis(hydroxido) derivatives [(C 5 R 5 )Mo(dppe)(OH) 2 ] [115], the structure of which was confirmed by X-ray diffraction for R = Et.…”

High Oxidation State Organometallic Chemistry in Aqueous Media: New Opportunities for Catalysis and Electrocatalysis

“…No knowledge was available on the stability of the Cp*ÀMo bond toward hydrolysis, nor on the nature of the MoO 3 moiety as a function of pH, nor on the redox properties in water. Organometallic oxomolybdenum compounds of different nuclearity in oxidation states lower than 6 have also been previously investigated, for example, [Mo + (mononuclear), [12,13] [Mo (dinuclear), [14,15] and [Mo 3 (Cp*) 3 …”

High Oxidation State Organometallic Chemistry in Aqueous Media: New Opportunities for Catalysis and Electrocatalysis.

“…Organometallic oxomolybdenum compounds of different nuclearity in oxidation states lower than 6 have also been previously investigated, e.g. Cp*Mo V OCl2 and [CpMo IV O(PMe3)2] + (mononuclear), [12,13] Cp2Mo V 2O4 and Cp*2Mo IV 2OCl4 (dinuclear), [14,15] [(Cp*Mo)3(2-OH)n(2-O)6-n] 2+ (n = 4,5,6) [16] and Cp3Mo IV 3OCl7 [17] (trinuclear). These compounds, however, have also been mainly investigated in organic solvents and their aqueous chemistry remains largely unexplored.…”