Chelate and Pincer Carbene Complexes of Rhodium and Platinum Derived from Hexaphenylcarbodiphosphorane, Ph3P=C=PPh3
详细信息 查看全文
- 作者：Kazuyuki Kubo ; Nathan D. Jones ; Michael J. Ferguson ; Robert McDonald ; and Ronald G. Cavell
- 刊名：Journal of the American Chemical Society
- 出版年：2005
- 出版时间：April 20, 2005
- 年：2005
- 卷：127
- 期：15
- 页码：5314 - 5315
- 全文大小：52K
- 年卷期：v.127,no.15(April 20, 2005)
- ISSN：1520-5126
文摘
The reaction of [(cod)RhCl]2 with Ph3P=C=PPh3 (1) gave the bidentate Rh(I) carbene complex, (cod)Rh[
2-C{P(C6H4)Ph2}{PPh3}] (2), in which one of the Ph groups in 1 underwent orthometalation to form the chelate. Displacement of cod by 2 equiv of PMe3 transformed 2, via a second orthometalation event, into the Rh(III) C,C,C pincer carbene complex, HRh(PMe3)2[3-C{P(C6H4)Ph2}2] (3). The reaction of [Me2Pt(SMe2)]2 with 1 led directly to the analogous C,C,C pincer carbene complex of Pt(II), (Me2S)Pt[3-C{P(C6H4)Ph2}2] (4). DFT calculations on a model form of 3 suggest a net single 
-bonding interaction between Rh and an sp2-hybridized carbene center, with a HOMO that is predominantly carbene pz in character.
2-C{P(C6H4)Ph2}{PPh3}] (2), in which one of the Ph groups in 1 underwent orthometalation to form the chelate. Displacement of cod by 2 equiv of PMe3 transformed 2, via a second orthometalation event, into the Rh(III) C,C,C pincer carbene complex, HRh(PMe3)2[3-C{P(C6H4)Ph2}2] (3). The reaction of [Me2Pt(SMe2)]2 with 1 led directly to the analogous C,C,C pincer carbene complex of Pt(II), (Me2S)Pt[3-C{P(C6H4)Ph2}2] (4). DFT calculations on a model form of 3 suggest a net single -bonding interaction between Rh and an sp2-hybridized carbene center, with a HOMO that is predominantly carbene pz in character.