25259-84-1Relevant academic research and scientific papers
Rhenium dihydrogen complexes and long H-H interactions: X-ray-determined single-crystal structures of ReCl(η2-H2)(Ph2PCH2CH 2PPh2)2·THF and [ReO2(Ph2PCHCHPPh2)2][ReO 4]
Kohli, Manu,Lewis, Dominic J.,Luck, Rudy L.,Silverton,Sylla
, p. 879 - 883 (2008/10/08)
Reduction of ReCl5 in tetrahydrofuran under Ar with 4 equiv of Na in the presence of bidentate tertiary phosphines (L2) yields complexes of the form ReCl(η2-H2) (L2)2, L2 = PPh2CH2CH2PPh2 (1), and L2 = PPh2CHCHPPh2 (2). A similar reduction of ReCl5 in the presence of the monodentate ligand PMe2Ph affords mixtures of ReH3(PMe2Ph)4 and the cation [ReH4(PMe2Ph)4]+. The metal-bonded H atoms in complexes 1 and 2 display T1 (min) times of 43(5) and 29(4) ms, respectively, at 200 MHz. This suggests a long H-H interaction. The single-crystal X-ray structures of complexes 1·THF and [ReO2(PPh2CHCHPPh2)2] [ReO4] (3) are reported. Crystal data: compound 1·THF, monoclinic, space group P21/c, a = 11.472(4) A?, b = 13.468(2) A?, β = 17.339(5) A?, β = 96.02(1)°, V = 2664.1(4) A?3, R = 2, R = 0.041 (Rw = 0.058) for 288 parameters and 2323 unique data having Fo > 3σ(Fo2); compound 3, triclinic, space group, P1, a = 9.946(1) A?, b = 11.744(3) A?, c = 12.506(2) A, α = 70.59(2)°, β = 73.46(1)°, γ = 65.72(1)°, V = 1237.0(3) A?3, Z = 1, R = 0.038 (Rw = 0.055) for 310 parameters and 2582 unique data having Fo > 3σ(Fo2). The geometries of 1 and the cation in 3 are those of distorted octahedra with the Re atoms situated on inversion points. In 1, there is 50% disorder between the trans Cl- and the η2-H2 (not located) ligands. Important distances for 1: Re-Cl at 2.574(6) A? and, Re-P(1) and Re-P(2) at 2.388(5) and 2.399(3) A?, respectively, with a P(1)-Re-P(2) angle of 80.3(1)°. Core distances for 3: Re-O(101) at 1.788(6) A? and Re-P(1) and Re-P(2) at 2.476(2) and 2.473(2) A?, respectively, with a P(1)-Re-P(2) angle at 81.18(8)°. The tetrahedral anion in 3, [ReO4]-, is located near an inversion point and was refined at 50% occupancy. Here Re-O bond distances range from 1.60(7) to 1.77(2) A?.
Decarbonylation of Methanol by Highly Reactive Rhenium Complexes
Bradley, Mark G.,Hofmann, Bruce R.
, p. 1180 - 1181 (2007/10/02)
The reaction of photogenerated (diphos = Ph2P2PPh2) with methanol gives decarbonylation under mild conditions and yields and .
