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A B–C Double Bond Unit Coordinated to Platinum: An Alkylideneboryl Ligand that Is Isoelectronic to Neutral Aminoborylene Ligands


  • This work was supported by the Deutsche Forschungsgemeinschaft. J.B. is grateful to the Fonds der Chemischen Industrie for a Ph.D. scholarship. S.S.S. thanks the Alexander von Humboldt Foundation for a postdoctoral fellowship.


The reaction of [Pt(PCy3)2] with Br2B-CH(SiMe3)2 resulted in generation of the first alkylideneboryl complex, trans-[Br(Cy3P)2Pt{B[DOUBLE BOND]CH(SiMe3)}], with concomitant elimination of Me3SiBr. The trans bromide ligand of the alkylideneboryl complex was readily substituted by a methyl group upon treatment with methyllithium, leading to another alkylideneboryl complex, trans-[Me(Cy3P)2Pt{B[DOUBLE BOND]CH(SiMe3)}]. Various spectrochemical techniques, single-crystal X-ray crystallography, and quantum chemical calculations confirmed the formulation of a double bond between the boron and the carbon atom. The theoretical studies also provided evidence for the stronger trans influence of the alkylideneboryl ligand over iminoboryl and oxoboryl ligands.

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