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1. Reactions of (polypyrazolylborato)(benzonitrile)rutheniums with terminal alkynes: Reactivity changeover by triethylamine toward arylalkyne polymerization or formation of (arylmethyl)(carbonyl) complexes

Author

Onishi, Masayoshi, Arikawa, Yasuhiro, Yamaguchi, Mamoru, Nagano, Tomoe, Inoue, Takayuki, Terasoba, Atsunobu, Matsuo, Suguru, Nakagawa, Maki, Kawano, Hiroyuki, Nagaoka, Junko, Umakoshi, Keisuke, and Furukawa, Mutsuhisa

Subjects
*ORGANORUTHENIUM compounds, *ALKYNES, *REACTIVITY (Chemistry), *TRANSITION metal complexes, *TRIETHYLAMINE, *POLYMERIZATION, *REACTION mechanisms (Chemistry), *INTERMEDIATES (Chemistry)
Abstract

Abstract: Reactions of (κ 3-polypyrazolylborato)(benzonitrile)rutheniums [RuCl{B(4-Ypz)4}(PhCN)2] {4-Ypz; 4-bromo-1-pyrazolyl (Y = Br) and 1-pyrazolyl (Y = H) groups} with terminal alkynes were studied. For the reactions with arylalkynes HCn the presence of NEt3, (arylmethyl)(carbonyl)rutheniums [Ru{CH2(aryl)}{B(4-Ypz)4}(CO)(PhCN)] were yielded, indicating alkyne Ceavage, whereas in the absence of NEt3, arylalkyne polymerization proceeded instead of the (arylmethyl)ruthenium formation. Reasonably attributed reaction mechanism shows significant role of the vinylidene intermediates “Ruh name="dbnd" />CH(aryl)”. [Copyright &y& Elsevier]

Published
2012
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