Molecular Structure of Co<sub>2</sub>(<i>μ</i>-Alkyne) Complex Containing Ph<sub>2</sub>PC<sub>5</sub>F<sub>6</sub>PPh<sub>2</sub>Ligand

• 作者: Makoto Minato Masaki Kakeya Yasutada Miyato
• 来源期刊: 有机化学国际期刊(英文)
• 学科: 化学
• 关键词: Alkyne-Bridged Cobalt COMPLEX Electron Deficient LIGAND Crystal Structure Coordinated ALKYNE C≡C Bond
• 年，卷（期）: yjhxgjqkyw,（2）
• 页码范围: 119-125
• 页数: 7页
• 分类号: O6

摘要

Oxidative-decarbonylation of Co2(CO) 6(μ-PhC≡CH) with Me3NO in the presence of an electron deficient ligand, Ph2PC5F6PPh2 (F6FOS), produces Co2 (CO) 4 (μ-PhC≡CH)(F6FOS), (1). The metrical values of 1 have been compared to those of the closely related cobalt carbonyl alkyne compound A containing (Z)-Ph2PCH=CHPPh2 (Z-dppe) ligand. Strikingly anomalous is an alkyne C≡C bond (1.34(1) ? in 1, which is somewhat elongated compared to A (1.31(1) ?). When taking a strong electron-withdrawing power of fluoride atom into account, F6FOS ligand appeared to reduce the π-back-donation ability of cobalt atom, making this bond shortened in comparison to the same bond in A. Bond lengthening in the alkyne C≡C bond in 1 is attributed to the enhanced electron donor ability of F6FOS compared to Z-dppe and can be understood by examining resonance structures of F6FOS ligand.