6533b82cfe1ef96bd128f5f6
RESEARCH PRODUCT
Mechanism of aminocarbene formation by nucleophilic attack on isocyanide ligands in platinum(II)2-pyrazyl and 4-pyridyl complexes
Franca Di BiancaPaolo UguagliatiFabiano VisentinBruno CrocianiLuciano Canovesesubject
ProtonChemistryLigandIsocyanideOrganic ChemistryKineticschemistry.chemical_elementPhotochemistryBiochemistryMedicinal chemistryNitrogenInorganic Chemistrychemistry.chemical_compoundNucleophileMaterials ChemistryAmine gas treatingPhysical and Theoretical ChemistryPlatinumdescription
Abstract The reactions of 2-pyrazyl and 4-pyridyl isocyanide complexes [Pt(CNC 6 H 11 )(C 4 H 3 N 2 - C 2 )(dppe)ClO 4 and [Pt(CNC 6 H 11 )(C 5 H 4 N- C 4 ) (dppe)]ClO 4 ( 1 ) with amines involving the formation of aminocarbene derivatives have been studied kinetically in 1,2-dichloroethane by UV—VIS techniques. The kinetics obey the simple second-order rate law rate = k 2 [ 1 ][amine]. Low activation enthalpies and highly negative activation entropies for the k 2 term are observed. A mechanism is proposed involving direct nucleophilic attack of the amine on the isocyanide carbon with concomitant proton transfer from the amine to the isocyanide nitrogen assisted by the heterocyclic nitrogen in position 1 of the 2-pyrazyl ligand.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 1997-05-01 |