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

Access to Document

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

Cite this

@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",

note = "Funding Information: This work was supported by Grant-in-aid for Scientific Research from the Ministry of Education, Science and Culture, Japan and the Sasakawa Scientific Research Grant from The Japan Science Society and JSPS Research Fellowships for Young Scientists. The authors thank Tosoh Akzo for supplying us with alkyl~duminum compounds.",

year = "1997",

month = dec,

day = "1",

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

language = "English",

volume = "547",

pages = "209--216",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "2",

}

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

N1 - Funding Information: This work was supported by Grant-in-aid for Scientific Research from the Ministry of Education, Science and Culture, Japan and the Sasakawa Scientific Research Grant from The Japan Science Society and JSPS Research Fellowships for Young Scientists. The authors thank Tosoh Akzo for supplying us with alkyl~duminum compounds.

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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U2 - 10.1016/S0022-328X(97)00375-6

DO - 10.1016/S0022-328X(97)00375-6

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AN - SCOPUS:0031521549

VL - 547

SP - 209

EP - 216

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

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