Monomeric five-coordinate rhenium diazenido and hydrazido complexes with aromatic thiolate ligands: X-ray structures of [Re(NNC6H4-Br)2(SC6H3-2,5-Me2)(PPh3)2] and [ReO(NNMePh)(SPh)3], and of the synthetic precursor [Re(NNC6H4-4-Br)2Cl(PPh3)2] |
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| Institution: | 1. Department of Mechanical and Aerospace Engineering, University at Buffalo, The State University of New York, Buffalo, NY 14260, United States;2. Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States;3. Research and Education in Energy Environment & Water Institute, University at Buffalo, The State University of New York, Buffalo, NY 14260, United States |
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| Abstract: | Reaction of ReOCl3(PPh3)2] with bromophenylhydrazine in methanol yields ReCl(N2C6H4Br)2(PPh3)2] (1). Complex 1 reacts with arylthiolates to give mixtures of Re(SAr)(N2C6H4Br)2(PPh3)2] (2) and Re2(SAr)7(NNR)2]−. Complexes 1 and 2 display trigonal bipyramidal geometries with the phosphine ligands occupying the axial sites. A significant feature of the structures is the nonequivalence of the rhenium-diazenido moieties, such that for 1 the ReN(1) and N(1)N(2) distances are 1.80(2) and 1.24(3) Å, while ReN(3) and N(3)N(4) are 1.73(2) and 1.32(3) Å, and for 2 the ReN distances are 1.73(1) and 1.80(2)° with corresponding NN distances of 1.32(2) and 1.25(2) Å. Reaction of (PPh4)ReO(SPh)4] (3) with unsymmetrically disubstituted hydrazines affords complexes of the type ReO(SPh)3(NMRR′)] (R = Me, R′ = Ph for 4). Complexes 3 and 4 display distorted square pyramidal geometries with the oxo groups apical. The significant feature of the structure of 4 is the nonlinear ReN(1)N(2) linkage, exhibiting an angle of 145.6(10)°. The angle does not appear to correlate with a significant contribution from a valence form with sp2 hybridization at the α-nitrogen. Crystal data: 1: monoclinic space group, P21/n, a = 12.216(2) Å, b = 19.098(2) Å, c = 20.257(4) Å, β = 106.20(1)°, V = 4538.3(8) Å3 to give Z = 4; structure solution and refinement based on 1905 reflections converged at R = 0.070. 2: monoclinic space group P21/n, a = 14.393(2) Å, b = 18.842(3) Å, c = 20.717(4)Å, β = 110.26(1)°, V = 5270.5(8) Å3 to give Z = 4 for D = 1.53 g cm−1; structure solution and refinement based on 4249 reflections to give R = 0.070. 3: monoclinic space group P21/n, a = 12.531(2) Å, b = 24.577(4) Å, c = 16.922(3) Å, β = 99.06(1)°, V = 5146.2(9) Å3, D = 1.36 g cm−3 for Z = 4, 2912 reflections, R = 0.050. 4: monoclinic space group p21/n, a = 16.137(2) Å, b = 9.863(2) Å, c = 16.668(2) Å, β = 111.12(1)°, V = 2474.7(6) Å3, D = 1.74 g cm−3 for Z = 4, 2940 reflections, R = 0.066. |
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