The synthesis, reactivity and modelling studies of [RuCl(CO)(η²-C,O-C₆H₄-2-CHO)(PPh₃)₂]: Crystal and molecular structures of [RuCl(CO)(η²-C,O-C₆H₄-2-CHO)(P

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• 作者：Kevin R. Flower ; Myles W. Garrould ; Laura G. Leal ; Claudia Mangold ; Patrick J. O’ ; Malley ; Robin G. Pritchard
• 关键词：Ruthenium ; Cyclometallation ; Aldehyde ; Crystal structure ; Density functional theory
• 刊名：Journal of Organometallic Chemistry
• 出版年：2008
• 出版时间：1 February 2008
• 年：2008
• 卷：693
• 期：3
• 页码：408-416
• 全文大小：541 K

文摘

Treatment of [RuHCl(CO)(PPh₃)₃] with Hg(C₆H₄-2-CHO)₂ in refluxing toluene gives [RuCl(CO)(η²-C,O-C₆H₄-2-CHO)(PPh₃)₂] ong>1ong> in good yield. Treatment of ong>1ong> with a stoichiometric amount of Ag[BF₄] in CH₂Cl₂/acetone (1:1) followed by either NCMe, ^tBuCN or ^tBuNC to give [Ru(L)(CO)(η²-C,O-C₆H₄-2-CHO)(PPh₃)₂][BF₄] ong>2ong>–ong>4ong> in excellent yields. All of the compounds ong>1ong>–ong>4ong> have been characterized by microanalysis, ¹H, ¹³C–{¹H} and ³¹P–{¹H} NMR spectroscopy. In addition compounds ong>1ong> and ong>3ong> have been characterized by single crystal X-ray diffraction studies and the cycloruthenated aldehyde Cwww.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>O bond length noticeably increases in the cationic system. The complexes [RuCl(CO)(η²-C,O-C₆H₄-2-CHO)(PH₃)₂] ong>1aong>, [Ru(NCCH₃)(CO)(η²-C,O-C₆H₄-2CHO)(PH₃)₂] ong>3aong>, [Ru(CNCH₃)(CO)(η²-C,O-C₆H₄-2CHO)(PH₃)₂] ong>4aong> [RuCl₂{Owww.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>C(H)Me}(CO)(PH₃)₂] ong>Xaong> and [RuCl₂{Owww.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>C(H)HCHwww.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>CH₂}(CO)(PH₃)₂] ong>XIaong> have also been modelled using DFT calculations (B3LYP LanL2DZ) and the minimized structures are qualitatively in good agreement with experimentally determined structures. In all cases the calculated Ru–L distances were longer than those observed by experiment, the trend of Ru–C_(metalated) did not model the crystallographically observed data and some disparity between the experimental and calculated Cwww.sciencedirect.com/scidirimg/entities/dbnd"" alt=""double bond; length as m-dash"" border=0>O bond length of the coordinated aldehyde is apparent.