3H-benzophosphepine complexes: Versatile phosphinidene precursors

Mark L.G. Borst, Rosa E. Bulo, Danièle J. Gibney, Yonathan Alem, Frans J.J. De Kanter, Andreas W. Ehlers, Marius Schakel, Martin Lutz, Anthony L. Spek, Koop Lammertsma

Research output: Contribution to journalArticlepeer-review

55 Citations (Scopus)

Abstract

The synthesis of a variety of benzophosphepine complexes [R = Ph, t-Bu, Me; MLn = W(CO)5, Mo(CO)5, Cr(CO)5, Mn(CO)2Cp] by two successive hydrophosphinations of 1,2-diethynylbenzene is discussed in detail. The first hydrophosphination step proceeds at ambient temperature without additional promoters, and subsequent addition of base allows full conversion to benzophosphepines. Novel benzeno-1,4-diphosphinanes were isolated as side products. The benzophosphepine complexes themselves serve as convenient phosphinidene precursors at elevated, substituent-dependent temperatures (> 55°C). Kinetic and computational analyses support the proposal that the phosphepine-phosphanorcaradiene isomerization is the rate-determining step. In the absence of substrate, addition of the transient phosphinidene to another benzophosphepine molecule is observed, and addition to 1,2-diethynylbenzene furnishes a delicate bidentate diphosphirene complex.

Original languageEnglish
Pages (from-to)16985-16999
Number of pages15
JournalJournal of the American Chemical Society
Volume127
Issue number48
DOIs
Publication statusPublished - 7 Dec 2005
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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