Synthesis of novel terminal iridium phosphinidene complexes

Arjan T. Termaten; Tom Nijbacker; Marius Schakel; Martin Lutz; Anthony L. Spek; Koop Lammertsma

doi:10.1021/om020062t

Synthesis of novel terminal iridium phosphinidene complexes

Arjan T. Termaten, Tom Nijbacker, Marius Schakel, Martin Lutz, Anthony L. Spek, Koop Lammertsma

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

65 Citations (Scopus)

Abstract

Stable, crystalline iridium-complexed phosphinidenes, Cp*(L)Ir=PR, are readily synthesized by (a) the reaction of Cp*(L)IrCl₂ (2, L = PPh₃) with LiPHMes* and (b) dehydrohalogenation of Cp*(PH₂R)IrCl₂ (5, R = Mes*, Is, Mes) with in situ capturing of transient Cp*Ir≢PR (4) with phosphines, phosphites, arsines, isocyanides, and carbon monoxide (L). Cp*Ir≢PR eluded direct detection. The X-ray crystal structures are reported for Cp*(PPh₃)Ir=PMes* (3) and Cp*(CO)Ir=PMes* (15). The more congested 3 has an E configuration for its Ir=P bond, whereas 15 is obtained in its Z form. The ³¹P NMR chemical shifts and ²Jpp coupling constants are diagnostic for the E and Z forms. More shielded phosphinidene resonances and larger coupling constants are typical for the E isomers. These iridium-complexed phosphinidenes react with gem-diiodides to form phosphaalkenes, but not with carbonyl groups.

Original language	English
Pages (from-to)	3196-3202
Number of pages	7
Journal	Organometallics
Volume	21
Issue number	15
DOIs	https://doi.org/10.1021/om020062t
Publication status	Published - 22 Jul 2002
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Synthesis of novel terminal iridium phosphinidene complexes",

abstract = "Stable, crystalline iridium-complexed phosphinidenes, Cp*(L)Ir=PR, are readily synthesized by (a) the reaction of Cp*(L)IrCl2 (2, L = PPh3) with LiPHMes* and (b) dehydrohalogenation of Cp*(PH2R)IrCl2 (5, R = Mes*, Is, Mes) with in situ capturing of transient Cp*Ir≢PR (4) with phosphines, phosphites, arsines, isocyanides, and carbon monoxide (L). Cp*Ir≢PR eluded direct detection. The X-ray crystal structures are reported for Cp*(PPh3)Ir=PMes* (3) and Cp*(CO)Ir=PMes* (15). The more congested 3 has an E configuration for its Ir=P bond, whereas 15 is obtained in its Z form. The 31P NMR chemical shifts and 2Jpp coupling constants are diagnostic for the E and Z forms. More shielded phosphinidene resonances and larger coupling constants are typical for the E isomers. These iridium-complexed phosphinidenes react with gem-diiodides to form phosphaalkenes, but not with carbonyl groups.",

author = "Termaten, {Arjan T.} and Tom Nijbacker and Marius Schakel and Martin Lutz and Spek, {Anthony L.} and Koop Lammertsma",

year = "2002",

month = jul,

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doi = "10.1021/om020062t",

language = "English",

volume = "21",

pages = "3196--3202",

journal = "Organometallics",

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TY - JOUR

T1 - Synthesis of novel terminal iridium phosphinidene complexes

AU - Termaten, Arjan T.

AU - Nijbacker, Tom

AU - Schakel, Marius

AU - Lutz, Martin

AU - Spek, Anthony L.

AU - Lammertsma, Koop

PY - 2002/7/22

Y1 - 2002/7/22

N2 - Stable, crystalline iridium-complexed phosphinidenes, Cp*(L)Ir=PR, are readily synthesized by (a) the reaction of Cp*(L)IrCl2 (2, L = PPh3) with LiPHMes* and (b) dehydrohalogenation of Cp*(PH2R)IrCl2 (5, R = Mes*, Is, Mes) with in situ capturing of transient Cp*Ir≢PR (4) with phosphines, phosphites, arsines, isocyanides, and carbon monoxide (L). Cp*Ir≢PR eluded direct detection. The X-ray crystal structures are reported for Cp*(PPh3)Ir=PMes* (3) and Cp*(CO)Ir=PMes* (15). The more congested 3 has an E configuration for its Ir=P bond, whereas 15 is obtained in its Z form. The 31P NMR chemical shifts and 2Jpp coupling constants are diagnostic for the E and Z forms. More shielded phosphinidene resonances and larger coupling constants are typical for the E isomers. These iridium-complexed phosphinidenes react with gem-diiodides to form phosphaalkenes, but not with carbonyl groups.

AB - Stable, crystalline iridium-complexed phosphinidenes, Cp*(L)Ir=PR, are readily synthesized by (a) the reaction of Cp*(L)IrCl2 (2, L = PPh3) with LiPHMes* and (b) dehydrohalogenation of Cp*(PH2R)IrCl2 (5, R = Mes*, Is, Mes) with in situ capturing of transient Cp*Ir≢PR (4) with phosphines, phosphites, arsines, isocyanides, and carbon monoxide (L). Cp*Ir≢PR eluded direct detection. The X-ray crystal structures are reported for Cp*(PPh3)Ir=PMes* (3) and Cp*(CO)Ir=PMes* (15). The more congested 3 has an E configuration for its Ir=P bond, whereas 15 is obtained in its Z form. The 31P NMR chemical shifts and 2Jpp coupling constants are diagnostic for the E and Z forms. More shielded phosphinidene resonances and larger coupling constants are typical for the E isomers. These iridium-complexed phosphinidenes react with gem-diiodides to form phosphaalkenes, but not with carbonyl groups.

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U2 - 10.1021/om020062t

DO - 10.1021/om020062t

M3 - Article

AN - SCOPUS:0013222906

SN - 0276-7333

VL - 21

SP - 3196

EP - 3202

JO - Organometallics

JF - Organometallics

IS - 15

ER -

Synthesis of novel terminal iridium phosphinidene complexes

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