Chelate and pincer carbene complexes of rhodium and platinum derived from hexaphenylcarbodiphosphorane, Ph3P=C=PPh3
Chelate and pincer carbene complexes of rhodium and platinum derived from hexaphenylcarbodiphosphorane, Ph3P=C=PPh3
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DOI：
10.1021/ja0502831
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发表时间：
2005-04-20
影响因子：
15
通讯作者：
Cavell, RG
中科院分区：
文献类型：
--
作者：
Kubo, K;Jones, ND;Cavell, RG
[(cod)RhCl]2与Ph3PCPPh3(1)反应得到二齿Rh(I)卡宾配合物，(cod)Rh[η2-C{P(C6H4)Ph2}{PPh3}](2)，其中1中的一个Ph基团发生邻位金属化形成螯合物。通过第二次邻位金属化事件，将 cod 替换为 2 当量的 PMe3transformed2，形成 Rh(III)C,C,Cpincer 卡宾复合物，HRh(PMe3)2[η3-C{P(C6H4)Ph2}2] (3)。 [Me2Pt(SMe2)]2 与 1 的反应直接生成 Pt(II) 的类似 C,C,C 夹卡宾配合物 (Me2S)Pt[η3-C{P(C6H4)Ph2}2] (4)。对 3 模型形式的 DFT 计算表明，Rh 和 sp2 杂化卡宾中心之间存在净单 σ 键相互作用，HOMO 主要是卡宾 pzin 特征。
The reaction of [(cod)RhCl]2with Ph3PCPPh3(1) gave the bidentate Rh(I) carbene complex, (cod)Rh[η2-C{P(C6H4)Ph2}{PPh3}] (2), in which one of the Ph groups in1underwent orthometalation to form the chelate. Displacement of cod by 2 equiv of PMe3transformed2, via a second orthometalation event, into the Rh(III)C,C,Cpincer carbene complex, HRh(PMe3)2[η3-C{P(C6H4)Ph2}2] (3). The reaction of [Me2Pt(SMe2)]2with1led directly to the analogousC,C,Cpincer carbene complex of Pt(II), (Me2S)Pt[η3-C{P(C6H4)Ph2}2] (4). DFT calculations on a model form of3suggest a net single σ-bonding interaction between Rh and an sp2-hybridized carbene center, with a HOMO that is predominantly carbene pzin character.