Oxidative addition of methyl iodide to monosubstituted and disubstituted derivatives of ruthenium pentacarbonyl: preparation of neutral and ionic complexes of ruthenium

Abstract

The oxidative addition of CH[sub 3]I to Ru(CO)[sub 4]PMe[sub 3] (1) gives the methyl complex Ru(CO)[sub 3]PMe[sub 3](CH[sub 3])I (3); with PMe[sub 3] complex 3 gives the acetyl complexes Ru(CO)[sub 2](PMe[sub 3])[sub 2](COCH[sub 3])I (isomers 10a and 10b), which, by decarbonylation, give Ru(CO)[sub 2](PMe[sub 3])[sub 2](CH[sub 3])I (4). Complex 4 can also be obtained by oxidative addition of CH[sub 3]I to Ru(CO)[sub 3](PMe[sub 3])[sub 2] (2). Complex 4 reacts at room temperature with the nucelotphiles CO, PMe[sub 3], and P(OMe)[sub 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 PMe[sub 3]) and complex 13 (in the case of P(OMe)[sub 3]). This last complex reacts with different nucleophiles (PMe[sub 3], P(OMe)[sub 3]) and gives the ionic tetraphosphine complexes [Ru(CO)(PMe[sub 3])[sub 3]P(OMe)[sub 3](CH[sub 3])]I (22) and [Ru-(CO)(PMe[sub 3])[sub 2](P(OMe)[sub 3])[sub 2](CH[sub 3])]BPh[sub 4] (24), respectively. The trisubstituted cyano derivative Ru(CO)(PMe[sub 3])[sub 2]P(OMe)[sub 3](CH[sub 3])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 basismore » of spectroscopic (IR, [sup 1]H, [sup 31]P, [sup 13]C) information. 45 refs., 1 fig., 3 tabs.« less