Carbon-oxygen bond formation on rhodium centers. Synthesis, characterization, crystal structure, and reactions of trans-PhORh(CO)(PPh sub 3 ) sub 2
- State Univ. of New York, Buffalo (USA)
The synthesis of a rhodium phenoxide is reported. The complex trans-PhORh(CO)(PPh{sub 3}){sub 2} crystallizes in the centrosymmetric monoclinic space group P2{sub 1}/c with a = 15.794 (3) {angstrom}, b = 11.449 (2) {angstrom}, c = 20.025 (3) {angstrom}, {beta} = 100.220 (13){degree}, V = 3,562 (1) {angstrom}{sup 3}, and Z = 4. Diffraction data (Mo K{alpha}, 2{theta} = 4.5-50.0{degree}) were collected with a Syntex P2{sub 1} diffractometer, and the structure was refined to R{sub F} = 2.8% for 5,293 reflections. The structure is isomorphous with the iridium analogue. Important dimensions include Rh-P = 2.337 (1)-2.357 (1) {angstrom}, Rh-CO = 1.801 (3) {angstrom} Rh-OPh = 2.044 (2) {angstrom}, and Rh-O-C(phenoxide) = 1.25.52 (19){degree}. This complex reacts with Ph{sub 2}CHC(O)Cl to give the ester Ph{sub 2}CHC(O)OPh and with MeI to give anisole, PhOMe. The formation of anisole from the rhodium phenoxide is in contrast to the failure to eliminate ethers from similar iridium complexes and is consistent with the known preference for elimination from second-row (rather than third-row) transition-metal complexes.
- OSTI ID:
- 6661703
- Journal Information:
- Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:1; ISSN 0276-7333; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
Similar Records
Dinuclear metal(O) complexes containing bridging or ligands. Synthesis, crystal structure and cyclic voltammetry of dinuclear Mo and W complexes, [Et{sub 4}N]{sub 3}[M{sub 2}(CO){sub 6}({mu}-OPh){sub 3}] (M = Mo, W)
Synthesis and characterization of manganese and rhenium metallacycles
Related Subjects
400200* -- Inorganic
Organic
& Physical Chemistry
BONDING
CARBON
CHALCOGENIDES
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
ELEMENTS
EXPERIMENTAL DATA
FABRICATION
INFORMATION
JOINING
MEASURING INSTRUMENTS
MEASURING METHODS
NONMETALS
NUMERICAL DATA
OXIDES
OXYGEN
OXYGEN COMPOUNDS
REFRACTORY METAL COMPOUNDS
RHODIUM COMPOUNDS
RHODIUM OXIDES
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS