Hydrometalation of PCBut and Activation of the P-C Bond by a Tetrairidium Carbonyl Cluster: Solution Characterization of [
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- 作者：Maria Helena Araujo ; Anthony G. Avent ; Peter B. Hitchcock ; John F. Nixon ; and Maria D. Vargas
- 刊名：Organometallics
- 出版年：1998
- 出版时间：December 7, 1998
- 年：1998
- 卷：17
- 期：25
- 页码：5460 - 5466
- 全文大小：245K
- 年卷期：v.17,no.25(December 7, 1998)
- ISSN：1520-6041
文摘
Reaction of [HIr4(CO)10(
-PPh2)], 1, with [Pt(dppe)(
2-PCBut)] yields four Ir4Pt clusters[Ir4Pt(dppe)(CO)n{-PC(H)But}(-PPh2)] (n = 10, 2, and 9, 3), [HIr4Pt(dppe)(-CO)(CO)7(-PCH2But)(-PPh2)], 4, and [Ir4Pt(dppe)(-CO)(CO)8(5-P)(-PPh2)], 5. These compoundscontain fragments arising from hydrometalation and cleavage of the P-C triple bond of thephosphaalkyne. The structures of compounds 2 and 3, isolated as a mixture, were proposedon the basis of multinuclear NMR and mass spectrometry. To our knowledge these are thefirst examples of clusters containing a phosphido fragment {-PC(H)But} originating fromhydrometalation of the phosphaalkyne. Compounds 4 and 5 were characterized in solutionby multinuclear NMR spectroscopy, and their solid-state structures were determined byX-ray analyses. A remarkably low 1JP-Pt coupling constant in the Pt(dppe) fragment of theformer square-based pyramidal compound is discussed.
-PPh2)], 1, with [Pt(dppe)(2-PCBut)] yields four Ir4Pt clusters[Ir4Pt(dppe)(CO)n{-PC(H)But}(-PPh2)] (n = 10, 2, and 9, 3), [HIr4Pt(dppe)(-CO)(CO)7(-PCH2But)(-PPh2)], 4, and [Ir4Pt(dppe)(-CO)(CO)8(5-P)(-PPh2)], 5. These compoundscontain fragments arising from hydrometalation and cleavage of the P-C triple bond of thephosphaalkyne. The structures of compounds 2 and 3, isolated as a mixture, were proposedon the basis of multinuclear NMR and mass spectrometry. To our knowledge these are thefirst examples of clusters containing a phosphido fragment {-PC(H)But} originating fromhydrometalation of the phosphaalkyne. Compounds 4 and 5 were characterized in solutionby multinuclear NMR spectroscopy, and their solid-state structures were determined byX-ray analyses. A remarkably low 1JP-Pt coupling constant in the Pt(dppe) fragment of theformer square-based pyramidal compound is discussed.