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
M3 - Article
AN - SCOPUS:0031521549
VL - 547
SP - 209
EP - 216
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 2
ER -