Dimolybdenum and Ditungsten Cyclopentadienyl Carbonyls with Electron-Rich Phosphido Bridges. Synthesis of the Hydrido Phosphido Complexes [M2Cp2(mg src="http://pubs.acs.org/
详细信息 查看全文
- 作者：M. Esther Garcí ; a ; Ví ; ctor Riera ; Miguel A. Ruiz ; M. Teresa Rueda ; and David Sá ; ez
- 刊名：Organometallics
- 出版年：2002
- 出版时间：December 9, 2002
- 年：2002
- 卷：21
- 期：25
- 页码：5515 - 5525
- 全文大小：203K
- 年卷期：v.21,no.25(December 9, 2002)
- ISSN：1520-6041
文摘
New hydrido complexes of the type [M2Cp2(
mages/entities/mgr.gif">-H)(mages/entities/mgr.gif">-PRR')(CO)4] (M = Mo, W) have beenprepared through the thermal reaction of [Mo2Cp2(CO)6] with HPCy2, H2PCy, or HPEt2 orthe thermal reaction of [W2Cp2(CO)4] with HPR2 (R = Cy, Et, Ph). In contrast, UV irradiationof [M2Cp2(CO)6] and HPRR' leads with good yield to the bis(phosphido) complexes [M2Cp2(mages/entities/mgr.gif">-PRR')2(mages/entities/mgr.gif">-CO)] (R = R' = Cy, Et, Ph; R = Cy, R' = H). Related complexes having differentphosphido groups, [M2Cp2(mages/entities/mgr.gif">-PR2)(mages/entities/mgr.gif">-PR'R' ')(mages/entities/mgr.gif">-CO)] (R = Cy, tBu, Ph; R' = Cy, tBu, Et; R' ' =Cy, tBu, Et, H), can be prepared in high yield through the photochemical reaction of [M2Cp2(mages/entities/mgr.gif">-PR2)(mages/entities/mgr.gif">-H)(CO)4] and HPR'R' ' or [M2Cp2(mages/entities/mgr.gif">-H)(mages/entities/mgr.gif">-PR'R' ')(CO)4] and HPR2. All triplybonded compounds react easily with carbon monoxide at room temperature or under moderateheating to finally yield the corresponding trans-dicarbonyl complexes [M2Cp2(mages/entities/mgr.gif">-PRR')2(CO)2]or [M2Cp2(mages/entities/mgr.gif">-PR2)(mages/entities/mgr.gif">-PR'R' ')(CO)2]. Some of the intermediates in these carbonylation reactionshave been identified, including the cis-dicarbonyl complex [Mo2Cp2(mages/entities/mgr.gif">-PPh2)(mages/entities/mgr.gif">-PtBu2)(CO)2]and the tricarbonyl complex [Mo2Cp2(mages/entities/mgr.gif">-PEt2)2(CO)3]. The structures of the new complexesare analyzed on the basis of the corresponding IR and NMR (1H, 31P, 13C) data, and thereaction pathways operative in these highly efficient syntheses of bis(phosphido) complexesis discussed on the basis of the available data and some cross-experiments.