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

Albertin; Albertin; Arikawa; Arikawa; Arikawa; Atsunobu Terasoba; Bianchini; Bianchini; Bianchini; Bruce; Bruce; Bruce; Bruneau; Bruneau; Bruneau; Bullock; Cadierno; Cadierno; Davies; Endres; Foley; Fukumoto; Fukumoto; Gemel; Gemel; Grotjahn; Halcrow; Hill; Hiroyuki Kawano; Ipaktschi; Johnson; Junko Nagaoka; Katayama; Katz; Kawano; Keisuke Umakoshi; Kostić; Lomprey; Maki Nakagawa; Mamoru Yamaguchi; Masayoshi Onishi; Matsuzawa; Melis; Merlic; Moreno; Murahashi; Mutsuhisa Furukawa; Onishi; Onishi; Onishi; Onishi; Puerta; Ritleng; Schmid; Selnau; Slugovc; Slugovc; Slugovc; Slugovc; Slugovc; Slugovc; Suguru Matsuo; Suzuki; Takahashi; Takahashi; Takayuki Inoue; Ting; Tokunaga; Tokunaga; Tomoe Nagano; Touchard; Touchard; Trofimenko; Trost; Trost; Trost; Wang; Werner; Wiedemann; Yasuhiro Arikawa; Yi; Zhu

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

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 HC≡C(aryl) in the presence of NEt 3, (arylmethyl)(carbonyl)rutheniums [Ru{CH 2(aryl)}{B(4-Ypz) 4}(CO)(PhCN)] were yielded, indicating alkyne C≡C bond cleavage, whereas in the absence of NEt 3, arylalkyne polymerization proceeded instead of the (arylmethyl)ruthenium formation. Reasonably attributed reaction mechanism shows significant role of the vinylidene intermediates "Ru=C=CH(aryl)"