Oxo-Bridged Bis(group 4 metal unsymmetric phosphonium-stabilized carbene) Complexes

Jia Yi Guo; Yuk Chi Chan; Yongxin Li; Rakesh Ganguly; Cheuk Wai So

doi:10.1021/om5012962

Oxo-Bridged Bis(group 4 metal unsymmetric phosphonium-stabilized carbene) Complexes

Jia Yi Guo, Yuk Chi Chan, Yongxin Li, Rakesh Ganguly, Cheuk Wai So^*

^*Corresponding author for this work

Nanyang Technological University

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

15 Citations (Scopus)

Abstract

The synthesis and reactivity of oxo-bridged bis(group 4 metal unsymmetric phosphonium-stabilized carbene) complexes are described. The reaction of [CH₂R^NR^S] (1; R^N = PPh₂NSiMe₃, R^S = PPh₂S) with 1 equiv of [M(NMe₂)₄] (M = Zr, Hf) afforded the group 4 metal unsymmetric phosphonium-stabilized carbene complexes [M(NMe₂)₂(CR^NR^S)] (M = Zr (4), Hf (5)). Their reactions with water in toluene afforded the oxo-bridged derivatives O[M(NMe₂)(CR^NR^S)]₂ (M = Zr (6), Hf (7)). Compound 6 underwent an insertion reaction with AdNCO to form O[Zr{OC(NMe₂)NAd}(CR^NR^S)]₂ (8; Ad = adamantyl). Compounds 4-8 were characterized by NMR spectroscopy and X-ray crystallography. (Chemical Presented).

Original language	English
Pages (from-to)	1238-1244
Number of pages	7
Journal	Organometallics
Volume	34
Issue number	7
DOIs	https://doi.org/10.1021/om5012962
Publication status	Published - Apr 13 2015
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Oxo-Bridged Bis(group 4 metal unsymmetric phosphonium-stabilized carbene) Complexes",

abstract = "The synthesis and reactivity of oxo-bridged bis(group 4 metal unsymmetric phosphonium-stabilized carbene) complexes are described. The reaction of [CH2RNRS] (1; RN = PPh2NSiMe3, RS = PPh2S) with 1 equiv of [M(NMe2)4] (M = Zr, Hf) afforded the group 4 metal unsymmetric phosphonium-stabilized carbene complexes [M(NMe2)2(CRNRS)] (M = Zr (4), Hf (5)). Their reactions with water in toluene afforded the oxo-bridged derivatives O[M(NMe2)(CRNRS)]2 (M = Zr (6), Hf (7)). Compound 6 underwent an insertion reaction with AdNCO to form O[Zr{OC(NMe2)NAd}(CRNRS)]2 (8; Ad = adamantyl). Compounds 4-8 were characterized by NMR spectroscopy and X-ray crystallography. (Chemical Presented).",

author = "Guo, {Jia Yi} and Chan, {Yuk Chi} and Yongxin Li and Rakesh Ganguly and So, {Cheuk Wai}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

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doi = "10.1021/om5012962",

language = "English",

volume = "34",

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T1 - Oxo-Bridged Bis(group 4 metal unsymmetric phosphonium-stabilized carbene) Complexes

AU - Guo, Jia Yi

AU - Chan, Yuk Chi

AU - Li, Yongxin

AU - Ganguly, Rakesh

AU - So, Cheuk Wai

PY - 2015/4/13

Y1 - 2015/4/13

N2 - The synthesis and reactivity of oxo-bridged bis(group 4 metal unsymmetric phosphonium-stabilized carbene) complexes are described. The reaction of [CH2RNRS] (1; RN = PPh2NSiMe3, RS = PPh2S) with 1 equiv of [M(NMe2)4] (M = Zr, Hf) afforded the group 4 metal unsymmetric phosphonium-stabilized carbene complexes [M(NMe2)2(CRNRS)] (M = Zr (4), Hf (5)). Their reactions with water in toluene afforded the oxo-bridged derivatives O[M(NMe2)(CRNRS)]2 (M = Zr (6), Hf (7)). Compound 6 underwent an insertion reaction with AdNCO to form O[Zr{OC(NMe2)NAd}(CRNRS)]2 (8; Ad = adamantyl). Compounds 4-8 were characterized by NMR spectroscopy and X-ray crystallography. (Chemical Presented).

AB - The synthesis and reactivity of oxo-bridged bis(group 4 metal unsymmetric phosphonium-stabilized carbene) complexes are described. The reaction of [CH2RNRS] (1; RN = PPh2NSiMe3, RS = PPh2S) with 1 equiv of [M(NMe2)4] (M = Zr, Hf) afforded the group 4 metal unsymmetric phosphonium-stabilized carbene complexes [M(NMe2)2(CRNRS)] (M = Zr (4), Hf (5)). Their reactions with water in toluene afforded the oxo-bridged derivatives O[M(NMe2)(CRNRS)]2 (M = Zr (6), Hf (7)). Compound 6 underwent an insertion reaction with AdNCO to form O[Zr{OC(NMe2)NAd}(CRNRS)]2 (8; Ad = adamantyl). Compounds 4-8 were characterized by NMR spectroscopy and X-ray crystallography. (Chemical Presented).

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JO - Organometallics

JF - Organometallics

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Oxo-Bridged Bis(group 4 metal unsymmetric phosphonium-stabilized carbene) Complexes

Abstract

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ASJC Scopus Subject Areas

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