Generation and reactivity of unsaturated iridium and rhodium dimethyl complexes

Journal Article · Wed Aug 01 00:00:00 EDT 1990 · Organometallics; (USA)

DOI:https://doi.org/10.1021/om00158a024· OSTI ID:6428935

Lundquist, E G; Folting, K; Huffman, J C; Caulton, K G ^[1]

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1. Indiana Univ., Bloomington (USA)

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.

• OSTI ID: 6428935
• Journal Information: Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:8; ISSN 0276-7333; ISSN ORGND
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
COMPLEXES
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
IRIDIUM COMPLEXES
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REACTIVITY
RHODIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES