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

Journal Article · Wed Mar 03 00:00:00 EST 1993 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00057a011· OSTI ID:6708701

Bellachioma, G; Cardaci, G; Macchioni, A; Madami, A ^[1]

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1. Universita di Perugia (Italy)

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 basis of spectroscopic (IR, [sup 1]H, [sup 31]P, [sup 13]C) information. 45 refs., 1 fig., 3 tabs.

• OSTI ID: 6708701
• Journal Information: Inorganic Chemistry; (United States), Vol. 32:5; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
CHEMICAL PREPARATION
ORGANOMETALLIC COMPOUNDS
RUTHENIUM COMPOUNDS
ABSORPTION SPECTROSCOPY
IONS
ISOMERIZATION
NUCLEAR MAGNETIC RESONANCE
OXIDATION
CHARGED PARTICLES
CHEMICAL REACTIONS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
REFRACTORY METAL COMPOUNDS
RESONANCE
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties