Molybdenum(0) Fischer ethoxycarbene complexes: Synthesis, X-ray crystal structures and DFT study

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• 作者：Armand Jansen van Rensburg^a ; Marilé ; Landman^a ; ^{marile.landman@up.ac.za} ; Petrus H. van Rooyen^a ; Marrigje M. Conradie^b ; Jeanet Conradie^b ; ^{conradj@ufs.ac.za}
• 关键词：Fischer carbene ; Molybdenum ; Triphenylphosphine ; Triphenylarsine ; DFT
• 刊名：Polyhedron
• 出版年：2017
• 出版时间：10 January 2017
• 年：2017
• 卷：121
• 期：Complete
• 页码：285-296
• 全文大小：2160 K
• 卷排序：121

文摘

The synthesis and structural investigations are presented of molybdenum(0) Fischer carbene complexes with general formula [L(CO)4MoC(OEt)(Ar)] with L = CO, PPh3, AsPh3 and Ar = 2-thienyl, 2-furyl, 2-(N-methyl)pyrrolyl, 2,2′-bithienyl. The X-ray crystal structures, along with NMR and IR spectroscopy, revealed a cis-orientation of the carbene and pnictogen ligands (PPh3 or AsPh3) for all the substituted complexes. A density functional theory study of all possible conformers indicated, in agreement with experimental results, that the cis-isomers (PPh3 or AsPh3cis relative to the carbene ligand) are more stable than the corresponding trans-isomers, and that most stable conformers have the aryl group syn to the ethoxy group for Ar = 2-thienyl, 2-(N-methyl)pyrrolyl, 2,2′-bithienyl and anti to the ethoxygroup for Ar = 2-furyl.