Reactivity of {Ru(C5Me5)[η2-P,O-Ph2PCH2C(tBu)=O](CO)}[PF6] towards Terminal Alkynes and Unexpected Rearrangement of a Fischer-Type Carbene Ligand

被引：1

作者：

Demerseman, Bernard ^{[1
]}

Toupet, Loic ^{[1
]}

机构：

[1] Univ Rennes 1, CNRS, UMR 6226, F-35042 Rennes, France

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2009年 / 28期

关键词：

Carbene ligands; Cyclopentadienyl ligands; Metallacycles; Phosphane ligands; Ruthenium; VINYLIDENE COMPLEXES; CRYSTAL-STRUCTURE; SUBSTITUTION; RUTHENIUM; DERIVATIVES; CHEMISTRY; CENTERS; OLEFINS; TOOL;

D O I：

10.1002/ejic.200900574

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The ruthenium complex {Ru(C5Me5)[eta(2)-P,O-Ph2PCH2C-(tBu)=O](CO)}[PF6] reacts with terminal alkynes HC CR (R = H, tBu, Ph) in methanol to afford {Ru[:C(OMe)-CH2R](C5Me5)[eta(1)-P-Ph2PCH2C(=O)tBu](CO)}[PF6] derivatives. The similar reaction conducted in dichloromethane as solvent led to six-membered metallacyclic complexes {Ru(C5Me5)[eta(2)-C,P-:C(CH2R)OC(tBu)=CH-PPh2](CO)}[PF6], which, when R is an aromatic group (R = Ph, p-tolyl), rearrange under moderate thermal activation into {Ru(C5Me5)[eta(2)-C,C,P-RCH=CH-OC(tBu)=CHPPh2](CO)}[PF6] derivatives, according to an isomerization of a Fischer-type carbene ligand into an eta(2)-coordinated vinylic ether, as shown by Xray single crystal analysis (R = p-tolyl). ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

引用

页码：4308 / 4313

页数：6

共 40 条

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