Oxidative addition of methyl iodide to monosubstituted and disubstituted derivatives of ruthenium pentacarbonyl: Preparation of neutral and ionic complexes of ruthenium
- 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), Journal Name: Inorganic Chemistry; (United States) Vol. 32:5; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
CARBONYLS
CHARGED PARTICLES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
IONS
ISOMERIZATION
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
REFRACTORY METAL COMPOUNDS
RESONANCE
RUTHENIUM COMPOUNDS
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS