66213-30-7Relevant academic research and scientific papers
THE PHOTOCHEMISTRY OR RHENIUM HYDRIDES. A FLASH PHOTOLYTIC INVESTIGATION OF THE TRANSIENTS IN THE PHOTOCHEMISTRY OF TRIS(DIMETHYLPHENYLPHOSPHINE)PENTAHYDRIDORHENIUM(V)
Muralidharan, S.,Ferraudi, G.,Green, Mark A.,Caulton, Kenneth G.
, p. 47 - 60 (1983)
The photochemistry of ReH5P3, (PPMe2Ph) has been investigated by laser and conventional flash photolysis.The first species observed in laser flash photolysis of the rhenium complex in saturated hydrocarbons has been assigned as an heptacoordinated 16-electron complex, ReH5P2, which is found to react with P at the diffusion-controlled rate.However, for photolysis in benzene such species is replaced by another metastable product, ReH5P2(C6H6), which is proposed to be a η2-C6H6 complex.At 10-5 M Re, isomerization and possibly elimination of hydrogen in subsequent unimolecular steps can precede dimerization, which has also been observed.The observed transient transformations have been correlated with previous observations during continuous photolysis, including coordination of simple olefins and H/D exchange of aenes.Kinetic measurements reveal that the transient ReH5P2 forms a dimetallic species by reaction with ReH5P3 and not with another (unsaturated) transient.
Dinuclear Elimination from Rhenium Hydrides and AlMe3: Rhenium/Aluminum Polyhydrides
Skupinski, Wincenty A.,Huffman, John C.,Bruno, Joseph W.,Caulton, Kenneth G.
, p. 8128 - 8136 (2007/10/02)
Reaction of Al2Me6 with ReH7P2 and with ReH5P3 (P = PMe2Ph and PMePh2) in benzene occurs with methane elimination to give ReH6AlMe2P2 and ReH4AlMe2P3, respectively.Each bimetallic compound is fluxional and shows evidence for both bridging and terminal hydride ligands.The X-ray crystal structure of ReH6AlMe2(PMePh2)2 shows it to be based on a ReH6P2 dodecahedron with AlMe2 bound to two hydride ligands, forming a η2-H2AlMe2 unit.Crystallographic data (-162 deg C): triclinic, P with Z = 2 and a = 17.815(8) Angstroem, b = 10.386(4) Angstroem, c = 11.094(4) Angstroem, α = 111.47(2) deg, β = 86.08(2) deg, γ = 95.78(2) deg.The X-ray crystal structure of ReH4AlMe2(PMePh2)3 shows a ReH4P3 pentagonal bipyramid (one P axial and two equatorial) with AlMe2 attached through three hydride ligands, one axial and two equatorial on Re, forming a H3AlMe22- unit.Crystallographic data (-164 deg C): monoclinic, P21/a with Z = 4 and a = 15.053(4) Angstroem, b = 15.900(4) Angstroem, c = 11.705(2) Angstroem, and β = 92.59(1) deg.Evidence for the mechanism of these reactions is presented, and the trend for aluminum to achieve a coordination number greater than 4 is surveyed.
