Synthesis and reactivity of Ph/sub 2/PCH/sub 2/PPh/sub 2/- (dppm-) stabilized Pd-Co and Pd-Pt-Co clusters. Effect of platinum versus palladium on the neighboring palladium center
The quantitative and regioselective synthesis of the mixed-metal cluster (PdPtCo/sub 2/(CO)/sub 7/(dppm)/sub 2/) (1b) was achieved by the reaction of the bimetallic complex (PdPtCl/sub 2/(dppm)/sub 2/) (dppm = /mu/-Ph/sub 2/PCH/sub 2/PPh/sub 2/) with (Co(CO)/sub 4/)/sup /minus//. As a result of phosphorus migration from palladium to cobalt, formal insertion of the Co(CO)/sub 3/ fragment into a metal-phosphorus bond of the precursor exclusively occurs into the more labile P /yields/ Pd bond. The lability of the exocyclic Co(CO)/sub 4/ fragment was evidenced and compared between 1b and (Pd/sub 2/Co/sub 2/(CO)/sub 7/(dppm)/sub 2/) (1a). Although a Pd-Co bond is involved, this lability is very sensitive to the neighboring metal center (Pd or Pt). Transmission of electronic effects from one metal-center to another was evidenced, and a platinum effect was observed in dissociating solvents, where 1a is partly dissociated but 1b is completely dissociated into (PdPtCo(CO)/sub 3/(S)(dppm)/sub 2/)(CO(CO)/sub 4/) (S = solvent). This is a reversible process, as is the equilibrium between 1 and halide anions. Solvento clusters were prepared that possess a labile coordination site on Pd leading to completely regioselective reactions with donor molecules, e.g., phosphines, CO, or C/sub 2/Ph/sub 2/. These ligands are labile (PR/sub 3/ < CO < C/sub 2/Ph/sub 2/ < MeCN < THF), and reversible CO uptake and substitution experiments showed that the Pd-bound CO in 4b is less labile than in 4a, indicating again a platinum effect on the reactive Pd center. The tris(bis(diphenylphosphino)methane) cationic cluster (Pd/sub 2/Co(CO)/sub 2/(dppm)/sub 3/)/sup +/ was isolated, in which all the metal-metal bonds are bridged by dppm ligands. Spectroscopic IR and /sup 1/H, /sup 31/P(/sup 1/H), and /sup 195/Pt(/sup 1/H) NMR data are discussed and confirm that in these reactions the PdMCo(dppm)/sub 2/ (M = Pd, Pt) framework is maintained.
- Research Organization:
- Universite Louis Pasteur, Strasbourg (France)
- OSTI ID:
- 5708148
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 27:8; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
BARYONS
CARBONYLS
CHEMICAL PREPARATION
COBALT COMPLEXES
COMPLEXES
DATA
DAYS LIVING RADIOISOTOPES
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
FERMIONS
HADRONS
HEAVY NUCLEI
HETEROCYCLIC COMPOUNDS
INFORMATION
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUCLEONS
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PALLADIUM COMPLEXES
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
PLATINUM 195
PLATINUM COMPLEXES
PLATINUM ISOTOPES
PROTONS
RADIOISOTOPES
RESONANCE
STABLE ISOTOPES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES