Synthesis and structure of the chiral dihydrogen complex trans-[Ru(eta(2)-H-2)H(R,R'-Me-DuPHOS)(2)]PF6 and the dinitrogen complex trans-[Ru(N-2)H(R,R'-Me-DuPHOS)(2)]PF6 (R,R'-Me-DuPHOS equals 1,2-bis((2R,5R)-2,5-dimethylphospholano)benzene)

被引：50

作者：

Schlaf, M ^{[1
]}

Lough, AJ ^{[1
]}

Morris, RH ^{[1
]}

机构：

[1] UNIV TORONTO,DEPT CHEM,LASH MILLER CHEM LABS,TORONTO,ON M5S 3H6,CANADA

来源：

ORGANOMETALLICS | 1997年 / 16卷 / 06期

关键词：

D O I：

10.1021/om960410p

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The complex [RuH(NH(2)NMe(2))(3)(cod)]PF6, cod = cyclooctadiene, a ruthenium hydride synthon, reacts with 2 equiv of R,R'-Me-DuPHOS, 1,2-bis((2R,5R)-2,5-dimethylphospholano)benzene, to produce the five-coordinate complex [RuH(R,R'-Me-DuPHOS)(2)]PF6. With H-2(g) this complex reversibly forms the dihydrogen complex trans-[Ru(eta(2)-H-2)H(R,R'-Me-DuPHOS)(2)]PF6. The T-1(min) at 400 MHz of 9.0 +/- 0.5 ms corresponds to an H-H distance of 0.78 Angstrom for fast motion of the eta(2)-H-2 ligand or 0.99 Angstrom for slow motion. The J(H,D) coupling value of the eta(2)-HD isotopomer is 30 Hz. By use of an empirical relationship this corresponds to an H-H distance of 0.92 Angstrom. The structure of trans-[Ru(eta(2)-H-2)H(R,R'-Me-DuPHOS)(2)]PF6 was determined by X-ray. It has approximate C-2 symmetry in the solid state and in solution, The eta(2)-H-2 ligand is located in a chiral pocket defined by the diphosphine ligands. The five-coordinate complex reacts with N-2 (1 atm) at -30 degrees C to give the thermally unstable complex trans-[Ru(N-2)H(R,R'-Me-DuPHOS)(2)]PF6, which was characterized by IR, NMR, elemental analysis, and X-ray diffraction.

引用

页码：1253 / 1259

页数：7

共 37 条

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