Theoretical and Experimental Investigation of Reaction Between a Cycloplatinated(II) Complex Containing Pyridine Ligand with Acyl Chloride

The reaction of cycloplatinated(II) complex [PtMe(bhq)(py)], 1, (bhqH = benzo[h]quinoline and py = pyridine) with acyl chloride gives the organoplatinum(IV) complex [PtCl(COMe)Me(bhq)(py)], POX. Attempts to grow crystals of the Pt(IV) complex POX in CH2Cl2 solvent forms the trichloro cycloplatinated(IV) complex [PtCl3(bhq)(py)], Pcryst, which its structure is determined by X-ray crystallography. The mechanism of the reactions is computationally investigated which suggest that first C-Cl bond of acyl chloride is oxidatively added to Pt(II) center of complex 1 through a cationic five-coordinate intermediate to give an octahedral Pt(IV) complex in which two new bonds, Pt-Cl and Pt-C(O)Me, are formed. In the resulted Pt(IV) complex, two Pt-Me and Pt-C(O)Me bonds are in the cis position to each other which increase the possibility of C-C reductive elimination. The energy barriers for both these two elementary reactions and structures are calculated using DFT calculations.

Theoretical and Experimental Investigation of Reaction Between a Cycloplatinated(II) Complex Containing Pyridine Ligand with Acyl Chloride Keywords:

platinum , Oxidative addition , Reductive elimination , DFT calculation , mechanisms