Generation and reactivity of unsaturated iridium and rhodium dimethyl complexes

Protonation (HBF{sub 4}{center dot}OEt{sub 2}) of MMe{sub 3}P{sub 3} (M = Rh, Ir; P = PMe{sub 2}Ph) in CH{sub 2}Cl{sub 2} gives CH{sub 4} and cis,mer-MMe{sub 2}P{sub 3}BF{sub 4}, characterized as a fluxional (methyl site exchange) molecular {eta}{sup 1}-BF{sub 4} species by {sup 1}H, {sup 31}P, {sup...

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Bibliographic Details
Published in:Organometallics 1990-08, Vol.9 (8), p.2254-2261
Main Authors: Lundquist, Eric G, Folting, Kirsten, Huffman, John C, Caulton, Kenneth G
Format: Article
Language:English
Subjects:
400201 - Chemical & Physicochemical Properties
COMPLEXES
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
IRIDIUM COMPLEXES
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REACTIVITY
RHODIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
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Summary:Protonation (HBF{sub 4}{center dot}OEt{sub 2}) of MMe{sub 3}P{sub 3} (M = Rh, Ir; P = PMe{sub 2}Ph) in CH{sub 2}Cl{sub 2} gives CH{sub 4} and cis,mer-MMe{sub 2}P{sub 3}BF{sub 4}, characterized as a fluxional (methyl site exchange) molecular {eta}{sup 1}-BF{sub 4} species by {sup 1}H, {sup 31}P, {sup 19}F, and {sup 11}B NMR studies and (for M = Ir) x-ray diffraction. Crystal data for IrMe{sub 2}P{sub 3}BF{sub 4}{center dot}C{sub 6}H{sub 6} ({minus}100{degree}C): a = 16.708 (6) {angstrom}, b = 9.332 (2) {angstrom}, c = 23.214 (8) {angstrom}, {beta} = 110.05 (2){degree}, with Z = 4 in space group P2{sub 1}/c. Ethylene replaces BF{sub 4}{sup {minus}} to give (at 25{degree}C) (IrMe{sub 2}(C{sub 2}H{sub 4})P{sub 3})BF{sub 4} and (at 50{degree}C) (Ir(C{sub 2}H{sub 4}){sub 2}P{sub 3})BF{sub 4} and C{sub 2}H{sub 6}. Ethylene reacts (25{degree}C) with RhMe{sub 2}P{sub 3}BF{sub 4} to immediately give ethane and (RhP{sub 4})BF{sub 4}. All of the above are characterized by multinuclear NMR and vibrational spectroscopy and, for (IrMe{sub 2}(C{sub 2}H{sub 4})P{sub 3})BF{sub 4}, X-ray diffraction.
ISSN:0276-7333
1520-6041
DOI:10.1021/om00158a024