Synthesis and reactions of Cp-linked phosphine complexes of rhodium
- Univ. of Rochester, NY (United States). Dept. of Chemistry
The linked Cp ligand [C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2}]{sup {minus}} has been used to synthesize several rhodium derivatives. Reaction with [RhClL{sub 2}]{sub 2} where L = C{sub 2}H{sub 4}, C{sub 8}H{sub 14}, or CO, gives ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}-CH{sub 2}PPh{sub 2})Rh(L) complexes, which have been characterized by single-crystal X-ray diffraction. Reaction of the ethylene complex with CO or PMe{sub 3} gives the carbonyl- and phosphine-substituted derivatives, respectively. Irradiation of the ethylene complex in the presence of hydrogen gives a new binuclear polyhydride, also structurally characterized, in which the chelating ligand spans the two metal centers. Reaction of the ethylene complex with iodine leads to the formation of the diiodide ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2})RhI{sub 2}, which in turn can be converted to the dihydride ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2})RhH{sub 2} by reaction with NaAl(OCH{sub 2}CH{sub 2}OCH{sub 3}){sub 2}H{sub 2}. The reactivity of the dihydride toward C-H bond activation has been investigated. While benzene does not give a stable oxidative addition adduct, pentafluorobenzene yields ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2})Rh(C{sub 6}F{sub 5})H, which was structurally characterized as its chloro derivative. Reaction of the dihydride with C{sub 6}F{sub 6} gives the {eta}{sup 2} complex ({eta}{sup 5}:{eta}{sup 1}-C{sub 5}H{sub 4}SiMe{sub 2}CH{sub 2}PPh{sub 2})Rh({eta}{sup 2}-C{sub 6}F{sub 6}), also structurally characterized.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-86ER13569
- OSTI ID:
- 655336
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 18 Vol. 17; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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