Preparation and reactions of Cp2HfRCl, Cp2HfRR′ and hafnacyclopent-2-enes

Yasushi Nishihara; Toyohisa Ishida; Shouquan Huo; Tamotsu Takahashi

doi:10.1016/S0022-328X(97)00375-6

Preparation and reactions of Cp₂HfRCl, Cp₂HfRR′ and hafnacyclopent-2-enes

Yasushi Nishihara, Toyohisa Ishida, Shouquan Huo, Tamotsu Takahashi

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

7 Citations (Scopus)

Abstract

Reaction of Cp₂HfCl₂ with R₃Al (R = Et, n-Pr, or n-Bu) in hexane selectively produced monoalkylhafnocene complexes, Cp₂HfRCl (1), in high yields. Cp₂HfMeCl (1a) was prepared by the reaction of oxo-bridged hafnocene complex (Cp₂HfCl)₂(μ-O) with Me₃Al. The treatment of 1 with alkylating reagents such as R′Li or EtMgBr afforded unsymmetrical dialkylhafnocene complexes Cp₂HfRR′ (3) in good to excellent yields. The kinetic study of thermolysis of Cp₂HfEtR (R = Me, Et, n-Bu, sec-Bu, t-Bu or Ph) suggested that decomposition of Cp₂HfEt(sec-Bu) was much faster than the others. Cp₂Hf(sec-Bu)₂ (2e) can be used as a good precursor of Cp₂Hf(II) species. Hafnacyclopent-2-enes (4) were prepared in good yields by the reaction of Cp₂HfEt₂ (2b) with alkynes.

Original language	English
Pages (from-to)	209-216
Number of pages	8
Journal	Journal of Organometallic Chemistry
Volume	547
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(97)00375-6
Publication status	Published - Dec 1 1997
Externally published	Yes

Keywords

Alkylhafnocene chloride
Dialkylhafnocene
Hafnacyclopent-2-ene
Hafnacyclopentadiene

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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@article{35ac0f4005db443a828f2b72f5666b6b,

title = "Preparation and reactions of Cp2HfRCl, Cp2HfRR′ and hafnacyclopent-2-enes",

abstract = "Reaction of Cp2HfCl2 with R3Al (R = Et, n-Pr, or n-Bu) in hexane selectively produced monoalkylhafnocene complexes, Cp2HfRCl (1), in high yields. Cp2HfMeCl (1a) was prepared by the reaction of oxo-bridged hafnocene complex (Cp2HfCl)2(μ-O) with Me3Al. The treatment of 1 with alkylating reagents such as R′Li or EtMgBr afforded unsymmetrical dialkylhafnocene complexes Cp2HfRR′ (3) in good to excellent yields. The kinetic study of thermolysis of Cp2HfEtR (R = Me, Et, n-Bu, sec-Bu, t-Bu or Ph) suggested that decomposition of Cp2HfEt(sec-Bu) was much faster than the others. Cp2Hf(sec-Bu)2 (2e) can be used as a good precursor of Cp2Hf(II) species. Hafnacyclopent-2-enes (4) were prepared in good yields by the reaction of Cp2HfEt2 (2b) with alkynes.",

keywords = "Alkylhafnocene chloride, Dialkylhafnocene, Hafnacyclopent-2-ene, Hafnacyclopentadiene",

author = "Yasushi Nishihara and Toyohisa Ishida and Shouquan Huo and Tamotsu Takahashi",

year = "1997",

month = dec,

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doi = "10.1016/S0022-328X(97)00375-6",

language = "English",

volume = "547",

pages = "209--216",

journal = "Journal of Organometallic Chemistry",

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TY - JOUR

T1 - Preparation and reactions of Cp2HfRCl, Cp2HfRR′ and hafnacyclopent-2-enes

AU - Nishihara, Yasushi

AU - Ishida, Toyohisa

AU - Huo, Shouquan

AU - Takahashi, Tamotsu

PY - 1997/12/1

Y1 - 1997/12/1

N2 - Reaction of Cp2HfCl2 with R3Al (R = Et, n-Pr, or n-Bu) in hexane selectively produced monoalkylhafnocene complexes, Cp2HfRCl (1), in high yields. Cp2HfMeCl (1a) was prepared by the reaction of oxo-bridged hafnocene complex (Cp2HfCl)2(μ-O) with Me3Al. The treatment of 1 with alkylating reagents such as R′Li or EtMgBr afforded unsymmetrical dialkylhafnocene complexes Cp2HfRR′ (3) in good to excellent yields. The kinetic study of thermolysis of Cp2HfEtR (R = Me, Et, n-Bu, sec-Bu, t-Bu or Ph) suggested that decomposition of Cp2HfEt(sec-Bu) was much faster than the others. Cp2Hf(sec-Bu)2 (2e) can be used as a good precursor of Cp2Hf(II) species. Hafnacyclopent-2-enes (4) were prepared in good yields by the reaction of Cp2HfEt2 (2b) with alkynes.

AB - Reaction of Cp2HfCl2 with R3Al (R = Et, n-Pr, or n-Bu) in hexane selectively produced monoalkylhafnocene complexes, Cp2HfRCl (1), in high yields. Cp2HfMeCl (1a) was prepared by the reaction of oxo-bridged hafnocene complex (Cp2HfCl)2(μ-O) with Me3Al. The treatment of 1 with alkylating reagents such as R′Li or EtMgBr afforded unsymmetrical dialkylhafnocene complexes Cp2HfRR′ (3) in good to excellent yields. The kinetic study of thermolysis of Cp2HfEtR (R = Me, Et, n-Bu, sec-Bu, t-Bu or Ph) suggested that decomposition of Cp2HfEt(sec-Bu) was much faster than the others. Cp2Hf(sec-Bu)2 (2e) can be used as a good precursor of Cp2Hf(II) species. Hafnacyclopent-2-enes (4) were prepared in good yields by the reaction of Cp2HfEt2 (2b) with alkynes.

KW - Alkylhafnocene chloride

KW - Dialkylhafnocene

KW - Hafnacyclopent-2-ene

KW - Hafnacyclopentadiene

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