A Molecular Rotor Possessing an H-M-H "Spoke" on a P-M-P "Axle": A Platinum(II) trans-Dihydride Spins Rapidly Even at 75 K

被引：23

作者：

Prack, Ernest ^{[1
]}

O'Keefe, Christopher A. ^{[2
]}

Moore, Jeremy K. ^{[3
]}

Lai, Angel ^{[1
]}

Lough, Alan J. ^{[4
]}

Macdonald, Peter M. ^{[1
]}

Conradi, Mark S. ^{[3
]}

Schurko, Robert W. ^{[2
]}

Fekl, Ulrich ^{[1
]}

机构：

[1] Univ Toronto, Mississauga, ON L5L 1C6, Canada

[2] Univ Windsor, Windsor, ON N9B 3P4, Canada

[3] Washington Univ, St Louis, MO 63130 USA

[4] Univ Toronto, Toronto, ON M5S 3H6, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 42期

基金：

加拿大创新基金会; 加拿大自然科学与工程研究理事会;

关键词：

GYROSCOPE-LIKE MOLECULES; METAL COORDINATION SPHERES; 3-SPOKE STATORS; PDX2/PTX2; ROTATORS; ALKENE METATHESIS; CRYSTAL-STRUCTURE; COMPLEXES; SUBSTITUTION; LIGANDS;

D O I：

10.1021/jacs.5b08213

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new class of low-barrier molecular rotors, metal trans-dihydrides, is suggested here. To test whether rapid rotation can be achieved, the known complex trans-H2Pt((PBu3)-Bu-t)(2) was experimentally studied by H-2 and Pt-195 solid-state NMR spectroscopy (powder pattern changes with temperature) and computationally modeled as a (Bu3P)-Bu-t-Pt-(PBu3)-Bu-t stator with a spinning H-Pt-H rotator. Whereas the related chloro-hydride complex, trans-H(Cl)-Pt((PBu3)-Bu-t)(2), does not show rotational behavior at room temperature, the dihydride trans-H2Pt((PBu3)-Bu-t)(2) rotates fast on the NMR time scale, even at low temperatures down to at least 75 K. The highest barrier to rotation is estimated to be similar to 3 kcal mol(-1), for the roughly 3 angstrom long rotator in trans-H2Pt((PBu3)-Bu-t)(2).

引用

页码：13464 / 13467

页数：4

共 35 条

[11] CHEMISTRY OF METAL-DIENE COMPLEXES - A CONVENIENT ONE-STEP SYNTHESIS OF MONO-PLATINUM(II) AND DIHYDRIDO-PLATINUM(II) COMPLEXES CONTAINING BULKY PHOSPHINE-LIGANDS FROM (COD)PTCL2 [J].