SYNTHESIS AND CHARACTERIZATION OF RHENIUM THIOLATE COMPLEXES - CRYSTAL AND MOLECULAR STRUCTURES OF [NBU(4)][REO(H2O)BR-4)]CENTER-DOT-2H(2)O, [BU(4)N][REOBR4(OPPH(3))], [REO(SC5H4N)(3)], [REO(SC4H3N2)(3)][REO(OH)(SC5H4N-3,6-(SIME(2)BU(T))(2))(2)], [RE

摘要

The syntheses and characterizations of six monomeric rhenium thiolate complexes and the structural characterization of two useful rhenium starting materials are presented. Pyridine-2-thiol (1) and its derivatives 3-(trimethylsilyl)pyridine-2-thiol (2), 3,6-bis(dimethyl-tert-butylsilyl)pyridine-2-thiol (3), and pyrimidine-2-thiol (4) were reacted with [Bu(4)N][ReOBr4(H2O)]. 2H(2)O (5), [Bu(4)N][ReOBr4(OPPh(3))] (6), [ReO2(C5H5N)(4)], and [Re{N2CO(C6H5)}Cl-2(PPh(3))(2)] to give [ReO(C5H4NS)(3)] (7), [ReO(C8H12NSiS)(3)] (8), [ReO(OH)(C11H20NSi2S)(2)] (9), [Re{N2CO(C6H5)}Cl(PPh(3))(2)(C5H4NS)] (10), [ReO(C4H3N2S)(3)] (11), and [Re{P(C6H5)(3)}(C4H3N2S)(3)] (12). Crystal data: 5, C16H42NO4Br4Re, tetragonal, I (4) over bar, a = 8.779(2) Angstrom, b = 11.614(2) Angstrom, c = 9.397(2) Angstrom, beta = 114.67(3)degrees, V = 870.7(4) Angstrom(3), Z = 2, 422 reflections, R = 0.0457; 6, C34H51NO2PBr4Re, triclinic, P (1) over bar, a = 14.437(3) Angstrom, b = 16.589(3) Angstrom, c = 16.783(3) Angstrom, alpha = 94.87(3)degrees, beta = 97.62(3)degrees, gamma = 93.80(3)degrees, V = 3957(2) Angstrom(3), Z = 4, 6141 reflections, R = 0.0758; 7, C15H12N3OS3Re, monoclinic, P2(1)/c, a = 11.533(2) Angstrom, b = 11.385(2) Angstrom, c = 14.039(3) (3) Angstrom, beta = 107.97(3)degrees, V = 1749.8(9) Angstrom(3), Z = 4, 1869 reflections, R = 0.0322; 9, C34H65N2O2S2Si4Re, triclinic, P (1) over bar, a = 8.072(2) Angstrom, b = 11.409(2) Angstrom, c = 12.402(3) Angstrom, alpha 79.67(3)degrees, beta = 74.05(3)degrees, gamma = 86.18(3)degrees, V = 1080.2(5) Angstrom(3), Z = 1, 4630 reflections, R = 0.0525; 10, C48H39N3OSP2ClRe, triclinic, P (1) over bar, a = 10.842(2) Angstrom, b = 13.660 (3) Angstrom, c = 17.665(4) Angstrom, alpha = 86.37(3)degrees, beta = 89.93(3)degrees, gamma = 77.22(3)degrees, V = 2080.2(10) Angstrom(3), Z = 2, 4329 reflections, R = 0.0437; 11, C12H9N6OS3Re, orthorhombic, Pbca, a = 8.240(2) Angstrom, b = 13.373(3) Angstrom, c = 29.388(6) Angstrom, V = 3238.4(16) Angstrom(3), Z = 8, 1400 reflections, R = 0.0512; 12, C31H26N6S3PCl2Re, triclinic, P (1) over bar, a = 9.224(2) Angstrom, b = 12.050(2) Angstrom, c = 17.665(4) Angstrom, alpha = 89.25(3)degrees, beta = 85.70(3)degrees, gamma = 67.94(3)degrees, V = 1604.0(8) Angstrom(3), Z = 2, 3592 reflections, R = 0.0697. [References: 67]