Synthesis and C-H activation reactions of ({eta}{sup 5}-indenyl)(trimethylphosphine)iridium alkyl and hydride complexes
- Univ. of California, Berkeley, CA (United States)
To obtain C-H oxidative addition products susceptible to further chemical transformation, the synthesis of a series of indenyliridium complexes that parallel the pentamethylcyclopentadienyl systems shown earlier to successfully activate alkane carbon-hydrogen bonds has been developed. Efficient routes to several members of the series ({eta}{sup 5}-C{sub 9}H{sub 7})IR(PMe{sub 3})(X)(Y), where X and Y are alkyl, aryl, and hydride ligands, are described. The structure of the (methyl)(phenyl)iridium complex (n{sup 5}-C{sub 9}H{sub 7})Ir(PMe{sub 3})(CH{sub 3})(Ph) (4b) has been determined by X-ray diffraction: space group P2{sub 1}/c with a = 7.6688 (6) {Angstrom}, b = 18.5650 (16) {Angstrom}, c = 12, 3855 (9) {Angstrom}, {alpha} = 90.0{degrees}, {beta} = 98.674 (7){degrees}, {gamma} = 90.0{degrees}, and Z = 4; R = 0.0164; R{sub w} = 0.0223 on the basis of 1972 data having F{sub 0}{sup 2}> 3{sigma}(F{sub o}{sup 2}). In spite of the increased lability of these complexes caused by the presence of the indenyl ligand, they retain both the thermal and photochemical C-H activating properties associated with the corresponding pentamethylcyclopentadienyl complexes. Thus ({eta}{sup 5}-C{sub 9}H{sub 7})Ir(PMe{sub 3})H{sub 2} (7) undergoes loss of H{sub 2} on irradiation and in benzene and cyclohexane solvent leads to ({eta}{sup 5}-C{sub 9}H{sub 7})Ir(PMe{sub 3})(C{sub 6}H{sub 5})(H) (6b) and ({eta}{sup 5}-C{sub 9}H{sub 7})Ir(PMe{sub 3})(C{sub 6}H{sub 11})(H) (6d), respectively. Thermolysis of ({eta}{sup 5}-C{sub 9}H{sub 7})Ir(PMe{sub 3})(CH{sub 3})(H) (6a) occurs to eliminate methane at a temperature lower than that for the Cp* analogue and in benzene and cyclohexane once again leads successfully to the phenyl and cyclohexyl hydrides 6b and 6d. 27 refs., 1 fig., 2 tabs.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 552720
- Journal Information:
- Organometallics, Vol. 11, Issue 5; Other Information: PBD: May 1992
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
CARBON
CHEMICAL BONDS
HYDRIDES
SYNTHESIS
CHEMICAL ACTIVATION
HYDROGEN
IRIDIUM COMPLEXES
IRRADIATION
QUANTITATIVE CHEMICAL ANALYSIS
MOLECULAR STRUCTURE
THERMODYNAMIC PROPERTIES
INFRARED SPECTRA
NMR SPECTRA
PHOTOCHEMICAL REACTIONS
CHEMICAL REACTION KINETICS
ALKYL RADICALS
BENZENE
LIGANDS
METHANE
X-RAY DIFFRACTION
ALKANES
CYCLOHEXANE