Preparation, Mechanism, and Structural Study of Group 6 Transition Metal 2-Substituted 3-Butadienyl Complexes: Crystal Stru

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• 作者：Annabelle G. W. Hodson and Grá ; inne Conole
• 刊名：Organometallics
• 出版年：1998
• 出版时间：November 23, 1998
• 年：1998
• 卷：17
• 期：24
• 页码：5347 - 5352
• 全文大小：151K
• 年卷期：v.17,no.24(November 23, 1998)
• ISSN：1520-6041

文摘

The complexes [WCl(CO)₂(G SRC="/images/gifchars/eta.gif" BORDER=0 >³-CH₂C(COX)C=CH₂)L₂] (X = Cl; L₂ = 2,2'-bipyridyl, 1,10-phenanthroline) (1) containing a 2-substituted butadienyl ligand were isolated from reactionsof Ph₄P[WCl(CO)₃L₂] and excess 1,4-dichlorobut-2-yne in chlorinated solvents. Spectroscopicevidence supports analogous reactions for the chromium analogue. Addition of 1 to alcohol,amine, or thiol (HX) gave good yields of the related ester (X = OMe), amide (X = NEt₂), orthiolate (X = SBuⁿ) complexes, respectively. Mechanisms and supporting evidence for theformation of 1 and the ester complex are proposed and discussed. Some differences inreactivity of Ph₄P[MCl(CO)₃L₂] with 1,4-dichlorobut-2-yne in methanol are reported for M= Mo and M = W. The structure of [WCl(CO)₂(ges/gifchars/eta.gif" BORDER=0 >³-CH₂C(COSBuⁿ)C=CH₂)(1,10-phenanthroline)] was confirmed by single-crystal X-ray diffraction analysis.