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Extended pi-Conjugation Systems Involving Highly Efficient d pi-p pi Interaction between Platinum(O) and Diphosphinidenecyclobutene Ligands

机译:延伸的PI-缀合系统涉及高效的D PI-P PI相互作用,铂(O)和二磷苯丁丁丁烯配体之间的相互作用

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Diphosphinidenecyclobutenes (DPCB-Y) bearing two sp~2-hybridized phosphorous atoms can operate as an effective pi-acceptor for late transition metals through pi-back donation from the metal d pi orbital to the low-lying pi* orbitals of the DPCB-Y ligands (d pi-p pi interaction). We recently succeeded in the synthesis and X-ray characterization of PtMe_2(DPCB) (Scheme 1). The dihedral angle between least-square planes b and a (or a') (23.2 deg ) is considerably smaller than that of free DPCB (av. 41.3 deg), showing the occurrence of pi-conjugation among the platinum, diphosphinidenecyclobutene, and two benzene rings. We report here the construction of more extended pi-conjugation systems by introducing some diarylacetylenes (tolan-R) and modifying DPCB.
机译:轴承两种SP〜2杂交的磷原子的二磷膦丁苯丁烷(DPCB-Y)可以作为晚期过渡金属的有效Pi-acceptor,通过从金属D PI轨道到DPCB的低位pi *轨道的PI-Back捐赠Y配体(D PI-P PI相互作用)。我们最近成功地完成了PTME_2(DPCB)的合成和X射线特征(方案1)。最小二平面B和A(或A')(23.2°)的二偏角角度远小于游离DPCB(AV.41.3℃),显示铂,二磷膦丁丁烯和两个中Pi缀合的发生。苯环。我们通过引入一些二芳基三丙烯酸乙烯(Tolan-R)并改性DPCB来报告更多扩展PI缀合系统。

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