钼-钼四重键的氧化断裂

Oxidative scission of a Mo-Mo quadruple bond.

作者信息

Cotton F A, Murillo C A, Zhou H C

机构信息

Laboratory for Molecular Structure and Bonding, Department of Chemistry, P.O. Box 30012, Texas A&M University, College Station, Texas 77842-3012, USA.

出版信息

Inorg Chem. 2000 Jul 24;39(15):3261-4. doi: 10.1021/ic000092t.

DOI:10.1021/ic000092t

PMID:11196863

Abstract

Two compounds containing the cations Mo2(DPhIP)4n+, n = 1 or 2 and DPhIP = the anion of 2,6-diphenyliminopiperidine, have been obtained by oxidation of the quadruply-bonded Mo2(DPhIP)4 species. The first oxidation process conserves the structure but results in a slight increase of the Mo-Mo distance from 2.114(1) to 2.136(2) A in Mo2(DPhIP)4.2CH2Cl2 (1.2CH2Cl2). However, the second oxidation process breaks the dimolybdenum bond, giving a bioctahedral complex, Mo2(DPhIP)42.5CH3CN.Et2O (2.5CH3CN.Et2O), with Mo...Mo separation of 2.9954(7) A. Crystallographic data for 1.2CH2Cl2 are space group C2/c, a = 17.1891(9) A, b = 17.807(1) A, c = 24.210(2) A, beta = 106.403(4) degrees, Z = 4; for 2.5CH3CN.Et2O, space group P2(1)/n, a = 16.523(5) A, b = 27.418(5) A, c = 18.163(3) A, beta = 93.48(2) degrees, Z = 4.

摘要

通过对四重键合的Mo₂(DPhIP)₄物种进行氧化，得到了两种含有阳离子Mo₂(DPhIP)₄ⁿ⁺（n = 1或2，DPhIP = 2,6 - 二苯基亚氨基哌啶的阴离子）的化合物。第一个氧化过程保留了结构，但使得Mo₂(DPhIP)₄·2CH₂Cl₂（1·2CH₂Cl₂）中Mo - Mo键距从2.114(1) Å略微增加至2.136(2) Å。然而，第二个氧化过程打破了二钼键，形成了一个双八面体配合物Mo₂(DPhIP)₄₂·5CH₃CN·Et₂O（2·5CH₃CN·Et₂O），Mo...Mo间距为2.9954(7) Å。1·2CH₂Cl₂的晶体学数据为：空间群C2/c，a = 17.1891(9) Å，b = 17.807(1) Å，c = 24.210(2) Å，β = 106.403(4)°，Z = 4；对于2·5CH₃CN·Et₂O，空间群P2(1)/n，a = 16.523(5) Å，b = 27.418(5) Å，c = 18.163(3) Å，β = 93.48(2)°，Z = 4。