Platinum thiolate complexes supported by PBP and POCOP pincer ligands as efficient catalysts for the hydrosilylation of carbonyl compounds.

Diphosphino-boryl-based PBP pincer platinum thiolate complexes, [Pt(SR){B(NCHPBu)-1,2-CH}] (R = H, 1a; Ph, 1b), and benzene-based bisphosphinite POCOP pincer platinum thiolate complexes, [Pt(SR)(BuPO)-1,3-CH] (R = H, 2a; Ph, 2b), were prepared and fully characterized by multinuclear NMR, X-ray crystallography, HRMS and elemental analyses. The application of these complexes in the catalytic hydrosilylation of aldehydes and ketones was investigated. It was found that these platinum thiolate complexes are efficient catalysts for the hydrosilylation of aldehydes and ketones at 65-75 °C.

The Stability of Diphosphino-Boryl PBP Pincer Backbone: PBP to POP Ligand Hydrolysis.

Since moisture may frequently be present in many solvents, it is important to know the reactivity of a catalyst against water for catalytic reactions. In order to explore the stability and understand the transformation process of diphosphino-boryl-based PBP pincer platform, [PdCl{B(NCH P Bu ) -o-C H }] (1) was treated with PdCl , HB(NCH PPh ) -o-C H was reacted with [PdCl (cod)] (cod=cyclo-octa-1,5-diene) and [Pd (dba) ] (dba=dibenzylideneacetone), respectively, in the presence of water. Some novel palladium POP complexes, [Pd Cl (μ-Cl){μ-κ -P,O,P-OB(NCH P Bu ) -o-C H }] (2 a), [Pd (μ-Cl) (μ-O) {μ-κ -P,O,P-OB(NCH PPh ) -o-C H } ] (2 b), [Pd {μ-κ -P,P,P,P-O(B(NCH PPh ) -o-C H ) }{μ-κ -P,P-(NHCH PPh ) -o-C H }] (3), were obtained.