TY - JOUR
T1 - Multiple Bonds between Main-Group Elements and Transition Metals. 91. High-Oxidation-State Rhenium Complexes Containing the Hydridotris(1-pyrazolyl)borato Ligand
AU - Degnan, Ian A.
AU - Behm, Joachim
AU - Cook, Malcolm R.
AU - Herrmann, Wolfgang A.
PY - 1991/5/1
Y1 - 1991/5/1
N2 - The rhenium(VII) complex [HB(pz)3]ReO3 (1) is readily reduced by triphenylphosphine in the presence of excess (CH3)3SiX (X = Br, Cl) to give the corresponding rhenium(V) complexes [HB(pz)3]ReOX2 (2, X = Cl; 3, X = Br, pz = pyrazolyl (C3H3N2)). [HB(pz)3]ReOCl2 (2), which seems to exist as two bond stretch isomers, reacts with 1 equiv of thiophenol in refluxing THF in the presence of a base [DBU or N(C2H5)3] to give [HB(pz)3]ReO(Cl)(SC6H5) (4). Two equivalents of thiophenol reacts with 2 in refluxing THF, also in the presence of base, to give [HB(pz)3]ReO(SC6H5)2 (5). 2 will react with 1,2-ethanedithiol or 1,2-benzenedithiol under similar conditions to give [HB(pz)3]ReO(S2C6H4) (6) and [HB(pz)3]ReO(S2C2H4) (7), respectively. The solid-state structures of 4 and 5 have been determined by X-ray crystallography. Both were found to be monomeric with an approximately octahedral arrangement of ligands around the rhenium atoms. 4 crystallizes in the orthorhombic space group Pbca (No. 61) with cell parameters a = 13.159 (1) Å, b = 18.656 (1) Å, c = 15.902 (1) Å, V= 3904 (1) Å3, Z = 8, R = 0.043, and Rw = 0.031 for 2713 reflections with I > 2σ(I). 5 crystallizes in the monoclinic space group P21/c (No. 14) with cell parameters a = 15.594 (3) Å, b = 21.624 (1) Å, c = 15.931 (1) Å, β = 107.00 (1)°, V= 5137 (1) Å3, Z = 4, R = 0.050, and Rw = 0.036 for 6683 reflections with I > 2σ(I).
AB - The rhenium(VII) complex [HB(pz)3]ReO3 (1) is readily reduced by triphenylphosphine in the presence of excess (CH3)3SiX (X = Br, Cl) to give the corresponding rhenium(V) complexes [HB(pz)3]ReOX2 (2, X = Cl; 3, X = Br, pz = pyrazolyl (C3H3N2)). [HB(pz)3]ReOCl2 (2), which seems to exist as two bond stretch isomers, reacts with 1 equiv of thiophenol in refluxing THF in the presence of a base [DBU or N(C2H5)3] to give [HB(pz)3]ReO(Cl)(SC6H5) (4). Two equivalents of thiophenol reacts with 2 in refluxing THF, also in the presence of base, to give [HB(pz)3]ReO(SC6H5)2 (5). 2 will react with 1,2-ethanedithiol or 1,2-benzenedithiol under similar conditions to give [HB(pz)3]ReO(S2C6H4) (6) and [HB(pz)3]ReO(S2C2H4) (7), respectively. The solid-state structures of 4 and 5 have been determined by X-ray crystallography. Both were found to be monomeric with an approximately octahedral arrangement of ligands around the rhenium atoms. 4 crystallizes in the orthorhombic space group Pbca (No. 61) with cell parameters a = 13.159 (1) Å, b = 18.656 (1) Å, c = 15.902 (1) Å, V= 3904 (1) Å3, Z = 8, R = 0.043, and Rw = 0.031 for 2713 reflections with I > 2σ(I). 5 crystallizes in the monoclinic space group P21/c (No. 14) with cell parameters a = 15.594 (3) Å, b = 21.624 (1) Å, c = 15.931 (1) Å, β = 107.00 (1)°, V= 5137 (1) Å3, Z = 4, R = 0.050, and Rw = 0.036 for 6683 reflections with I > 2σ(I).
UR - http://www.scopus.com/inward/record.url?scp=33751499379&partnerID=8YFLogxK
U2 - 10.1021/ic00009a039
DO - 10.1021/ic00009a039
M3 - Article
AN - SCOPUS:33751499379
SN - 0020-1669
VL - 30
SP - 2165
EP - 2170
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 9
ER -