The synthesis and chemistry of organoiridium allyl and oxo complexes
Cp*Ir(eta/sup 3/-C/sub 3/H/sub 5/)H (2, Cp* = eta/sup 5/-C/sub 5/Me/sub 5/) was cleanly synthesized. Thermolysis of 2 in benzene in the presence of phosphines produced Cp*(PR/sub 3/)Ir(n-C/sub 3/H/sub 7/)(C/sub 6/H/sub 5/) (R = Me, Ph), and in hydrocarbon solvents gave substituted ..pi..-allyliridium hydride species. Two mono- and dinuclear cyclometallated complexes were isolated. Thermolysis of Cp*(eta/sup 3/-C/sub 3/H/sub 5/)IrH in concentrated benzene solutions produced Cp*(C/sub 6/H/sub 5/)Ir(..mu..-H)(eta/sup 1/,eta/sup 3/-C/sub 3/H/sub 4/)IrCp*. The structure was determined crystallographically. Addition of dative ligands to 1 produced benzene and Cp*(L)Ir(eta/sup 1/,eta/sup 3/-C/sub 3/H/sub 4/)IrCp* (2-6, L = PMe/sub 3/, CO, CH/sub 2/=CH/sub 2/, P(OMe/sub 3/)/sub 3/ and t-BuNC). Thermolysis of the PMe/sub 3/ complex 2 gave rise to the intramolecular C-H bond activation product. Addition of LiEt/sub 3/BH to Cp*(PMe/sub 3/)(eta/sup 1/-C/sub 3/H/sub 5/)IrCl produces the iridacyclobutane complex Cp*(PMe/sub 3/)IrCH/sub 2/CH/sub 2/CH/sub 2/. Dehydration of (Cp*Ir(..mu..-OH)/sub 3/IrCp*)/sup +/OAc/sup -/ with amine bases generated the bis-..mu..-oxo complex (Cp*IrO)/sub 2/. Addition of PPh/sub 3/ to 1 produced O=PPh/sub 3/ and Cp*(PPh/sub 3/)Ir(..mu..-O)Cp*Ir. The structure was determined crystallographically. 22 refs., 23 figs., 4 tabs.
- Research Organization:
- Lawrence Berkeley Lab., CA (USA)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5528123
- Report Number(s):
- LBL-24230; ON: DE88004558
- Country of Publication:
- United States
- Language:
- English
Similar Records
C-H insertion and. pi. -complex formation reactions of (/eta//sup 5/-C/sub 5/Me/sub 5/)(PMe/sub 3/)Ir with ethylene: an intra- and intermolecular isotope effect study
C-H oxidative addition and reductive elimination reactions in a dinuclear iridium complex
Related Subjects
400201* -- Chemical & Physicochemical Properties
ACETONITRILE
ACTIVATION ENERGY
ALKANES
ALKYL RADICALS
ALLYL RADICALS
AROMATICS
BENZENE
CHEMICAL BONDS
CHEMICAL PREPARATION
CHEMICAL PROPERTIES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
CRYSTALLOGRAPHY
CYCLOALKANES
ENERGY
HYDRIDES
HYDROCARBONS
HYDROGEN COMPOUNDS
IRIDIUM COMPLEXES
IRIDIUM COMPOUNDS
IRIDIUM HYDRIDES
KINETICS
LIGANDS
MASS SPECTRA
NITRILES
NMR SPECTRA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SOLVENTS
ORGANOMETALLIC COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PROPANE
RADICALS
REACTION INTERMEDIATES
REACTION KINETICS
REFRACTORY METAL COMPOUNDS
SOLVENTS
SPECTRA
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
YIELDS