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

21 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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10.1021/ja9048509

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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",

number = "37",

}

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.

UR - https://www.scopus.com/pages/publications/70349394355

U2 - 10.1021/ja9048509

DO - 10.1021/ja9048509

M3 - Article

C2 - 19702264

AN - SCOPUS:70349394355

SN - 0002-7863

VL - 131

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

ASJC Scopus subject areas

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