Low-valent Organorhenium Compounds

Electronic Structure of ReO3Me by Variable Photon Energy Photoelectron Spectroscopy, Absorption Spectroscopy and Density Functional Calculations

“…Rather, is it the Re−O moieties which characterize the majority of the chemistry displayed. ReO 3 Me is a highly versatile oxidizing agent in organic chemistry, with alkene epoxidation, Baeyer−Villiger reactions, and aromatic oxidation being readily effected through intermediate peroxo derivatives which permit oxidation to proceed while preserving the parent Re−O moieties. , However, the Re−C bond does play an pivotal role in alkene metathesis, for which ReO 3 Me and related Re(VII) species have been shown to have high activity. , This reaction is generally considered to proceed by the mechanism proposed by Chauvin, involving the intermediacy of alkylidene complexes, with the ReC moiety being regenerated in the catalytic cycle. , Hence, rather than M−C bond fission, it is the formation of a rhenium−carbon double bond which facilitates alkene metathesis. Indeed, matrix-isolated ReO 3 Me has been shown to tautomerize to such a methylidene species under the influence of UV light. , Hence, the strength, stability, and covalent nature of the Re−C bond in ReO 3 Me endow it with a chemistry markedly different from that displayed by its counterpart in TiCl 3 Me.…”

Synthesis, Structure, and Fluxionality of (μ-Diphenylsilylene)(fulvalene)tetracarbonyldirhenium Double Si−H Activation to the First Fulvalene Silylene Complex

“…As part of an effort aimed at effecting multiple C−H activations on FvM 2 systems, we turned to [FvRe 2 (CO) 6 ] ( 1 ) and report here a model study featuring double Si−H activation to give the title compound. Complex 1 has been made previously and remains virtually unexplored, which is surprising, considering the rich chemistry of [CpRe(CO) 3 ] . Of particular relevance to the present study is the photolysis of the latter in the presence of silanes which results in decarbonylated products of oxidative addition, [CpRe(CO) 2 (SiR 3 )H] …”

Mono‐ and Dinuclear Rhenium Polyhydride Complexes Bearing the Chelating Ligand 1,2‐Bis(dicyclohexylphosphanyloxy)ethane

“…[8] They can also undergo a variety of thermal, photochemical or oxidative substitution reactions in which H 2 is replaced by a two-electron donor. [9] Although many rhenium polyhydride complexes of phosphanes are known, less attention has been given to complexes of phosphites [P(OR) 3 ], phosphonites [PR 1 (OR) 2 ] and phosphinites [PR 2 (OR) 1 ].…”