Oxidative addition of methyl iodide to monosubstituted and disubstituted derivatives of ruthenium pentacarbonyl: preparation of neutral and ionic complexes of ruthenium
作者:Gianfranco Bellachioma、Giuseppe Cardaci、Alceo Macchioni、Andrea Madami
DOI:10.1021/ic00057a011
日期:1993.3
The oxidative addition of CH3I to Ru(CO)4PMe3 (1) gives the methyl complex Ru(CO)3PMe3(CH3)I (3); with PMe3 complex 3 gives the acetyl complexes Ru(CO)2(PMe3)2(COCH3)I (isomers 10a and 10b), which, by decarbonylation, give Ru(CO)2(PMe3)2(CH3)I (4). Complex 4 can also be obtained by oxidative addition of CH3I to Ru(CO)3(PMe3)2 (2). Complex 4 reacts at room temperature with the nucleophiles CO, PMe3, and P(OMe)3 giving the acetyl complexes (structures 7, 15, and 18, respectively), which at higher temperatures isomerize to 8, 16, and 19, respectively. Decarbonylation of these complexes gives complex 4 (in the case of CO), complex 12 (in the case of PMe3), and complex 13 (in the case of P(OMe)3). This last complex reacts with different nucleophiles (PMe3, P(OMe)3) and gives the ionic tetraphosphine complexes [Ru(CO)(PMe3)3P(OMe)3(CH3)]I (22) and [Ru(CO)(PMe3)2(P(OMe)3)2(CH3)]BPh4 (24), respectively. The trisubstituted cyano derivative Ru(CO)(PMe3)2P-(OMe)3(CH3)CN (14) is obtained by the reaction of complex 22 with KCN in acetone. The structures of the various complexes were assigned, in most cases, on the basis of spectroscopic (IR, H-1, P-31, C-13) information.