Metallorganische Lewis-Saeuren XXXIV. Kationische Pentacarbonyl(isocyanid)rhenium(I)-Komplexe und deren Reaktionen mit Nucleophilen

Article abstract of DOI:10.1016/0022-328X(88)80531-X

Pentacarbonyl(tetrafluoroborato)rhenium, (OC)5ReFBF3, reacts with isocyanides to give the ionic complexes <(OC)5ReCNR>⁺BF4^- (1) (R=CMe3, C6H11, Ph, CH2CO2Et, CH2SO2C6H4Me).The reactivity of 1 with nucleophiles (N3^-, OH^-, OR^-, NH2R, NHR2) has been studied.In complexes 1 with R=CMe3, C6H11, Ph, nucleophilic attack occurs at the carbon monoxide ligand to give the compounds cis-(OC)4Re(CNR)NCO (R=CMe3, Ph), cis-(OC)4Re(CNR)COOH (R=CMe3, C6H11), cis-(OC)4Re(CNCMe3)CO2R' (R'=Me, Et), cis-(OC)4Re(CNCMe3)CONHR' (R'=CH2Ph, (CH2)3OH), cis-(OC)4Re(CNCMe3)CONR'2 (2R'=(CH2)4, respectively.Reaction of 1 with ethylene diamine, 1,6-diaminohexane or piperazine gives the dicarbamoyl-bridged complexes Me3CNC(OC)4ReCONH(CH2)nNHCORe(CO)4CNCMe3 (n=2,6) and Me3CNC(OC)4ReCON(CH2CH2)2NCORe(CO)4CNCMe3.In complexes 1 (R=CH2CO2Et, CH2SO2C6H4Me) hydroxide adds to the carbon atom of the isocyanide ligand to yield the pentacarbonylcarbamoyl complexes, (OC)5ReCONHR.