23136-99-4Relevant academic research and scientific papers
Oxygen and chlorine atom transfer between tungsten, molybdenum, and rhenium complexes. Competition between one- and two-electron pathways
Over, Diana E.,Critchlow, Susan C.,Mayer, James M.
, p. 4643 - 4648 (2008/10/08)
Inter-metal oxygen atom transfer reactions between molybdenum, tungsten, and rhenium complexes are described. With only chloride and PMePh2 as supporting ligands, oxygen atom transfer is observed from rhenium to molybdenum and tungsten and from
Synthesis and structure of seven-coordinate rhenium(III) mixed halo-phosphine isocyanide complexes
Warner, Steve,Cheatham, Linda K.,Tulip, Thomas H.,Williams, Ian D.,Lippard, Stephen J.
, p. 1221 - 1226 (2008/10/08)
The synthesis of mixed halo-phosphine isocyanide complexes of general formula [ReCl2(CNR)3(PMePh2)2]+ is described. The crystal structure of a representative member of this class, [ReCl2(CN-t-Bu)3(PMePh2)2](SbF 6) (1), has been determined. This complex adopts the C2υ capped trigonal prismatic geometry with close nonbonded contacts of 2.341 (8) and 2.330 (9) A? between coordinated isocyanide carbon atoms. Such distances in seven-coordinate compounds reveal that they are good candidates for reductive coupling of the isocyanide ligands, a reaction previously studied for 1. The syntheses of [ReCl3(CN-t-Bu)2(PMePh2)2] and [ReCl3(CN-2,6-Me2Ph)3(PMePh2)] are also reported. Red crystals of [Re(O)(OEt)Cl2(PMePh2)2] (2) were isolated in 25% yield as a side product during the preparation of [ReCl3(PMePh2)3] starting material from AgReO4. The identity of 2 was established by IR spectroscopy, elemental analysis, and X-ray crystallography. The Re-O bond distance of 1.699 (5) A? is characteristic of a metal-oxygen triple bond. Crystal data: for 1, a = 10.486 (2) A?, b = 13.201 (2) A?, c = 17.559 (2) A?, α = 76.21 (1)°, β = 89.73 (1)°, γ = 87.05 (1)°, triclinic, P1 (Ci1; Z = 2); for 2, a = 11.015 (1) A?, b = 12.745 (1) A?, c = 21.035 (3) A?, β = 105.19 (1)°, monoclinic, P21/n (C2h5; Z = 4).
Reduction of ReCl5 in the presence of PMePh2 to give mer-ReCl3(PMePh2)3, ReCl(η2-H2)(PMePh2)4, ReH3(PMePh2)4, or ReCl(CO)3(PMePh2)2, depending on conditions
Cotton, F. Albert,Luck, Rudy L.
, p. 2181 - 2186 (2008/10/08)
Reduction of ReCl5 with excess magnesium in a THF/toluene (1:1) mixture in the presence of PMePh2 leads to the formation of mer-ReCl3(PMePh2)3 (1) in high yields. However, reduction with 4 equiv of Na affords ReCl(η2-H2)(PMePh2)4 (2), and when an excess of Na is employed, ReH3(PMePh2)4 (3) is obtained. The complex ReCl(CO)3(PMePh2)2 (4) is formed when solutions of 2 are placed under a CO atmosphere. The variable-temperature 1H and 31P NMR spectra of 2 and 3 are reported. The single-crystal X-ray structures of complexes 1 and 3 are reported. Crystal data: compound 1, monoclinic, space group P21/c, a = 11.429 (3) A?, b = 17.468 (6) A7ring;, c = 23.189 (6) A?, β = 97.88 (2)°, V = 4585 (7) A?3, Z = 4, R = 0.053 (Rw = 0.062) for 365 parameters and 2424 unique data having Fo > 3σ(Fo2); compound 3, triclinic, space group P1, a = 10.745 (4) A?, b = 22.136 (4) A?, c = 10.361 (2) A?, α = 98.51 (2)°, β = 109.12 (2)°, γ = 98.38 (2)°, V = 2252 (1) A?3, Z = 2, R = 0.054 (Rw = 0.093) for 447 parameters and 7440 unique data having Fo > 3σ(Fo2). The geometry of 3 is that of a distorted pentagonal bipyramid with PMePh2 ligands in the apical positions. The metal-bonded hydrogen atoms were located in the difference maps and refined to give an average Re-H distance of 1.76 [2] A? and a closest H-H distance of 1.96 (13) A?.
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.
