Synthesis, characterization, and reactivity of. cap alpha. -ketoacyl complexes of platinum(II) and palladium(II). Crystal structures of trans-Pt(PPh/sub 3/)/sub 2/(Cl)(COCOPh) and cis-Pt(PPh/sub 3/)/sub 2/(COPh)(COOMe)
The ..cap alpha..-ketoacyl chloro complexes, trans-M(PPh/sub 3/)/sub 2/(Cl)(COCOR) (M = Pt: R = Ph, 1a; R = p-FC/sub 6/H/sub 4/, 1b; R = p-ClC/sub 6/H/sub 4/, 1c; R = p-MeC/sub 6/H/sub 4/, 1d; R = Me, 1e. M = Pd: R = Ph, 2), were synthesized by the oxidative addition of the appropriate ..cap alpha..-ketoacyl chloride with either Pt(PPh/sub 3/)/sub 4/ or Pd(PPh/sub 3/)/sub 4/. The crystal structure of 1a showed a square-planar geometry around the Pt with the two carbonyl groups virtually coplanar and in an s-trans configuration. The above compounds were found to decompose thermally to the corresponding benzoyl compounds, trans-M(PPh/sub 3/)/sub 2/(Cl)(COR). A detailed kinetic study of the decarbonylation of 1a and 2 indicated the presence of two competing pathways, one of which involved the initial dissociation of a PPh/sub 3/ ligand. The kinetic and thermodynamic parameters for the various steps in the mechanism were determined.
- Research Organization:
- Pennsylvania State Univ., University Park
- DOE Contract Number:
- FG02-84ER13295
- OSTI ID:
- 6951908
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:1; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
BOND ANGLE
BOND LENGTHS
CATIONS
CHARGED PARTICLES
CHEMICAL PREPARATION
CHEMICAL PROPERTIES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
COUPLING CONSTANTS
CRYSTAL STRUCTURE
DATA
DIMENSIONS
EXPERIMENTAL DATA
INFORMATION
INFRARED SPECTRA
IONS
ISOTOPES
KETONES
KINETICS
LENGTH
LIGHT NUCLEI
MAGNETIC RESONANCE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PALLADIUM COMPLEXES
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
PLATINUM COMPLEXES
REACTION KINETICS
RESONANCE
SPECTRA
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES