ELUCIDATION OF THE STRUCTURES OF THE HYDRIDOTHIOLATO COMPLEXES WH(SC6H2PR3I-2,4,6)(3)(L)(PME(2)PH), L=PME(2)PH OR PYRIDINE, BY NMR AND X-RAY TECHNIQUES

被引:4
作者
BURROW, TE
LOUGH, AJ
MORRIS, RH
RICHARDS, RL
机构
[1] UNIV TORONTO,DEPT CHEM,TORONTO,ON M5S 1A1,CANADA
[2] UNIV SUSSEX,NITROGEN FIXAT LAB,BRIGHTON BN1 9QR,E SUSSEX,ENGLAND
来源
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE | 1995年 / 73卷 / 07期
关键词
MOLYBDENUM; TUNGSTEN; THIOLATE; HYDRIDE; NMR; NOE;
D O I
10.1139/v95-135
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Measurement of the T-1 values of the P-31 nuclei in the unusual capped trigonal bipyramidal complexes WH(tipt)(3)(PMe(2)Ph)(2) (1, tipt = SC6H2Pr3i-2,4,6) and W(H-2)(tipt)(3)(PMe(2)Ph)(2) allows the determination of the phosphorus-hydride distance of 2.2 +/- 0.2 Angstrom and the P-W-H angle of about 62 +/- 7 degrees. An approximate location of the hydride on an S2P face is proposed on the basis of steric interactions. The crystal structure of WH(tipt)(3)-(NC5H5)(PMe(2)Ph) (2) is reported; the WS3NP core consists of a distorted trigonal bipyramidal system with the phosphine and pyridine ligands axial and the thiolate ligands equatorial. The hydride ligand was not located by X-ray diffraction but can be positioned on an open S2P face at an angle P-W-H of about 65 degrees. The small P-W-H angle results in large (2)J(H,P) coupling for 1 and 2. The H-1 NMR spectrum of complex 2 is assigned by use of NOE and homodecoupling NMR methods. This complex has the same crowded structure in solution as in the crystalline state. The pyridine ligand, which is sandwiched between two tipt aryl groups, is hindered from rotating around the W-N bond.
引用
收藏
页码:1092 / 1101
页数:10
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