TY - JOUR
T1 - Some Pentamethylcyclopentadienyl-Ruthenium Derivatives of Methyl Propiolate
AU - Bruce, M.I.
AU - Hall, B.C.
AU - Skelton, Brian
AU - Tiekink, E.R.T.
AU - White, Allan
AU - Zaitseva, N.N.
PY - 2000
Y1 - 2000
N2 - The reaction between methyl propiolate and RuCl(PPh3)(2)Cp* and NH4PF6 in EtOH gives cationic vinylidene [Ru{=C=CH(CO2Me)}(PPh3)2Cp*][PF6] (1), which is deprotonated to Ru(C=CCO2Me)(PPh3)(2)Cp* by NaOMe. The alkynyl complex reacts with PhCH2Br to give [Ru{=C=C(CH2Ph)(CO2Me)}(PPh3)(2)Cp*](+), isolated as its bromide and PF6- salts. In contrast, reactions between methyl propiolate and RuCl(PPh3)(2)Cp* in benzene afford neutral vinylidene RuCl{=C=CH(CO2Me)}(PPh3)Cp* (4) and metallacycle RuCl{CH=C(CO2Me)CH=C(CO2Me)}(PPh3)Cp* (5). The former complex is dehydrochlorinated by NaOMe in the presence of MeCN or P(OMe)(3) to give Ru(C=CCO2Me)(L)(PPh3)Cp* [L = MeCN and P(OMe)(3), respectively]. A minor product (2%), obtained from treatment of (5) with NaOMe, is Ru{CH=C(CO2Me)CH=C(CO2Me)C=CHC(O)OMe}(CO)(PPh3)(2) (8). X-Ray crystal structures of complexes (1), (4), (5) and (8) are reported.
AB - The reaction between methyl propiolate and RuCl(PPh3)(2)Cp* and NH4PF6 in EtOH gives cationic vinylidene [Ru{=C=CH(CO2Me)}(PPh3)2Cp*][PF6] (1), which is deprotonated to Ru(C=CCO2Me)(PPh3)(2)Cp* by NaOMe. The alkynyl complex reacts with PhCH2Br to give [Ru{=C=C(CH2Ph)(CO2Me)}(PPh3)(2)Cp*](+), isolated as its bromide and PF6- salts. In contrast, reactions between methyl propiolate and RuCl(PPh3)(2)Cp* in benzene afford neutral vinylidene RuCl{=C=CH(CO2Me)}(PPh3)Cp* (4) and metallacycle RuCl{CH=C(CO2Me)CH=C(CO2Me)}(PPh3)Cp* (5). The former complex is dehydrochlorinated by NaOMe in the presence of MeCN or P(OMe)(3) to give Ru(C=CCO2Me)(L)(PPh3)Cp* [L = MeCN and P(OMe)(3), respectively]. A minor product (2%), obtained from treatment of (5) with NaOMe, is Ru{CH=C(CO2Me)CH=C(CO2Me)C=CHC(O)OMe}(CO)(PPh3)(2) (8). X-Ray crystal structures of complexes (1), (4), (5) and (8) are reported.
U2 - 10.1071/CH99099
DO - 10.1071/CH99099
M3 - Article
SN - 0004-9425
VL - 53
SP - 99
EP - 107
JO - Australian Journal of Chemistry
JF - Australian Journal of Chemistry
IS - N/A
ER -