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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
Department of Materials Chemistry, Graduate School of Engineering, Yokohama National University, Yokohama, Japan
Department of Materials Chemistry, Graduate School of Engineering, Yokohama National University, Yokohama, Japan
Department of Materials Chemistry, Graduate School of Engineering, Yokohama National University, Yokohama, Japan
- 1 Department of Materials Chemistry, Graduate School of Engineering, Yokohama National University, Yokohama, Japan
- 2 Department of Materials Chemistry, Graduate School of Engineering, Yokohama National University, Yokohama, Japan
- 3 Department of Materials Chemistry, Graduate School of Engineering, Yokohama National University, Yokohama, Japan
International Journal of Organic Chemistry·Volume 05 (2015)·Pages 119–125·Published 25 May 2015·DOI10.4236/ijoc.2015.52013
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Abstract
Oxidative-decarbonylation of Co 2 (CO) 6 ( μ -PhC≡CH) with Me 3 NO in the presence of an electron deficient ligand, Ph 2 PC 5 F 6 PPh 2 (F 6 FOS), produces Co 2 (CO) 4 ( μ -PhC≡CH)(F 6 FOS), (1). The metrical values of 1 have been compared to those of the closely related cobalt carbonyl alkyne compound A containing (Z)-Ph 2 PCH=CHPPh 2 (Z-dppe) ligand. Strikingly anomalous is an alkyne C≡C bond (1.34(1) Å in 1, which is somewhat elongated compared to A (1.31(1) Å). When taking a strong electron-withdrawing power of fluoride atom into account, F 6 FOS 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 F 6 FOS compared to Z-dppe and can be understood by examining resonance structures of F 6 FOS ligand.
KeywordsAlkyne-Bridged Cobalt ComplexElectron Deficient LigandCrystal StructureCoordinated Alkyne C≡C Bond
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