Iridium phosphinidene complexes: A comparison with iridium imido complexes in their reaction with isocyanides

Halil Aktas; Jos Mulder; Frans J.J. De Kanter; J. Chris Slootweg; Marius Schakel; Andreas W. Ehlers; Martin Lutz; Anthony L. Spek; Koop Lammertsma

doi:10.1021/ja9048509

Iridium phosphinidene complexes: A comparison with iridium imido complexes in their reaction with isocyanides

Halil Aktas, Jos Mulder, Frans J.J. De Kanter, J. Chris Slootweg, Marius Schakel, Andreas W. Ehlers, Martin Lutz, Anthony L. Spek, Koop Lammertsma

Research output: Contribution to journal › Article › peer-review

19 Citations (Scopus)

Abstract

18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cp*(Xy-N≡C)Ir=PAr] (Ar = Mes*, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cp*(Xy-N≡C)IrPArC=NR]. Their structures were ascertained by X-ray diffraction. Density functional theory investigations on model structures revealed that the iridaphosphirane complexes are formed from the addition of the isocyanide to 16-electron species [Cp*Ir=PAr] forming first complex 3 that subsequently reacts with another isocyanide to give the products following a different pathway than its nitrogen analogue [Cp*Ir≡Nt-Bu] 1.

Original language	English
Pages (from-to)	13531-13537
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	131
Issue number	37
DOIs	https://doi.org/10.1021/ja9048509
Publication status	Published - 23 Sept 2009
Externally published	Yes

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{876f8aba4bed4366b3a8443a33023124,

title = "Iridium phosphinidene complexes: A comparison with iridium imido complexes in their reaction with isocyanides",

abstract = "18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cp*(Xy-N≡C)Ir=PAr] (Ar = Mes*, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cp*(Xy-N≡C)IrPArC=NR]. Their structures were ascertained by X-ray diffraction. Density functional theory investigations on model structures revealed that the iridaphosphirane complexes are formed from the addition of the isocyanide to 16-electron species [Cp*Ir=PAr] forming first complex 3 that subsequently reacts with another isocyanide to give the products following a different pathway than its nitrogen analogue [Cp*Ir≡Nt-Bu] 1.",

author = "Halil Aktas and Jos Mulder and {De Kanter}, {Frans J.J.} and Slootweg, {J. Chris} and Marius Schakel and Ehlers, {Andreas W.} and Martin Lutz and Spek, {Anthony L.} and Koop Lammertsma",

year = "2009",

month = sep,

day = "23",

doi = "10.1021/ja9048509",

language = "English",

volume = "131",

pages = "13531--13537",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Iridium phosphinidene complexes

T2 - A comparison with iridium imido complexes in their reaction with isocyanides

AU - Aktas, Halil

AU - Mulder, Jos

AU - De Kanter, Frans J.J.

AU - Slootweg, J. Chris

AU - Schakel, Marius

AU - Ehlers, Andreas W.

AU - Lutz, Martin

AU - Spek, Anthony L.

AU - Lammertsma, Koop

PY - 2009/9/23

Y1 - 2009/9/23

N2 - 18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cp*(Xy-N≡C)Ir=PAr] (Ar = Mes*, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cp*(Xy-N≡C)IrPArC=NR]. Their structures were ascertained by X-ray diffraction. Density functional theory investigations on model structures revealed that the iridaphosphirane complexes are formed from the addition of the isocyanide to 16-electron species [Cp*Ir=PAr] forming first complex 3 that subsequently reacts with another isocyanide to give the products following a different pathway than its nitrogen analogue [Cp*Ir≡Nt-Bu] 1.

AB - 18-Electron nucleophilic, Schrock-type phosphinidene complexes 3 [Cp*(Xy-N≡C)Ir=PAr] (Ar = Mes*, Dmp, Mes) are capable of unprecedented [1 + 2]-cycloadditions with 1 equiv of isocyanide RNC (R = Xy, Ph) to give novel iridaphosphirane complexes [Cp*(Xy-N≡C)IrPArC=NR]. Their structures were ascertained by X-ray diffraction. Density functional theory investigations on model structures revealed that the iridaphosphirane complexes are formed from the addition of the isocyanide to 16-electron species [Cp*Ir=PAr] forming first complex 3 that subsequently reacts with another isocyanide to give the products following a different pathway than its nitrogen analogue [Cp*Ir≡Nt-Bu] 1.

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DO - 10.1021/ja9048509

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AN - SCOPUS:70349394355

SN - 0002-7863

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SP - 13531

EP - 13537

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 37

ER -

Iridium phosphinidene complexes: A comparison with iridium imido complexes in their reaction with isocyanides

Abstract

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