Structural studies and matrix photochemistry of tetramethyloxorhenium(vi), (CH3)4ReO, and related compounds

The chemistry of the carbon–transition metal double and triple bond: annual survey covering the year 2002

“…Rhenium carbene complexes (e.g. 576, Scheme 61) were generated from low-temperature matrix photolysis of either tetramethyloxorhenium (575) or trimethyldioxorhenium [547,548]. The methylidene complex was determined to be the primary photoproduct and was assigned on the basis of its infrared spectrum in comparison with the vibrational spectrum calculated by DFT.…”

Matrix photochemistry of ethyltrioxorhenium(VII), C2H5ReO3: Tautomerisation via β-hydrogen migration with the sequential formation of two different ethene derivatives

“…Extending the matrix studies to other alkyloxorhenium compounds, viz. (CH 3 ) 3 ReO 2 [14] and (CH 3 ) 4 ReO [15], has made clear that formation of an alkylidene derivative of rhenium is a common, but not necessarily exclusive, reaction channel. This, then, is the context in which we report on the studies we have carried out on the matrix photochemistry of C 2 H 5 ReO 3 , 1.…”

“…Individual molecules have been monitored and identified by their IR spectra, the conclusions being endorsed (i) by the response to complete or selective deuterium substitution, (ii) by comparison of the wavenumbers and intensities in IR absorption of the vibrational features with those deduced by DFT calculations, and (iii) by analogies with the measured spectra of related Re@O and Re-AOH derivatives, e.g. H 2 CRe(OH)O 2 [11], H 2 CRe(CH 3 )O 2 [14], H 2 CRe(CH 3 ) 2 O [15], OReF 4 [16] and O 2 ReF 3 [17], and of ethene and its complexes [18] under comparable conditions. Hence the primary reaction induced by UV-visible irradiation will be shown to involve tautomerisation of 1 giving not the alkylidene hydroxo derivative CH 3 (H)C@Re(OH)O 2 (as the behaviour of CH 3 ReO 3 [11] might lead one to expect) but two ethene complexes of Re(OH)O 2 , 2 and 3, formed sequentially via b-hydrogen elimination.…”

Catalysis and Organometallic Chemistry of Monometallic Species

“…142- 144 The study and reactivity of alkyl rhenium oxides including the structure and vibrational properties of [ReEtO 3 ] have been investigated by electron diffraction, X-ray crystallography, IR spectroscopy and DFT calculations. 145 147 has shown evidence for rhenium methylidene species relevant to the use of this class of complex as metathesis catalysts. Reactivity studies of methyl rhenium() oxo complexes that catalyse the sulfoxidation of thioethers to sulfoxides have also been isolated.…”