User-Friendly Platinum Catalysts for the Highly Stereoselective Hydrosilylation of Alkynes and Alkenes.

With a view to addressing the shortcomings of traditional catalysts, a new generation of outstanding N-heterocyclic carbene platinum(0) complexes for the hydrosilylation of unsaturated carbon-carbon bonds is reported. Their discovery and application to the stereoselective addition of various silanes to silylated alkynes, terminal acetylenes, and olefins is presented. Insights into the catalytic cycle and the origin of the stereoselectivity are also discussed.

Highly enantioselective hydroformylation of dihydrofurans catalyzed by hybrid phosphine-phosphonite rhodium complexes.

Unprecedented regio- and enantioselectivities (>91%) are reported for the Rh-catalyzed asymmetric hydroformylation of 2,3- and 2,5-dihydrofuran using tunable hybrid phosphine-phosphonite ligands.

IPr* an easily accessible highly hindered N-heterocyclic carbene.

Herein, we wish to describe the efficient three-step synthesis of a novel highly hindered, but flexible, N-heterocyclic carbene and its coordination chemistry to Ag(i) and Rh(i).

Structure and reactivity of a unique Y-shaped tricoordinate bis(silyl)platinum(II)-NHC complex.

Y not? A unique, three-coordinate Y-shaped bis(silyl)platinum(II) complex was isolated and characterized (see structure; C light gray, N blue, Si pink, Pt dark gray). DFT studies on a model system shed light on the nature of this unusual coordination mode for platinum(II).

Palladium-catalyzed cyclopropanation of alkenyl silanes by diazoalkanes: evidence for a Pd(0) mechanism.

Alkenyl silanes are efficiently converted to the corresponding silyl cyclopropanes in the presence of a slight excess of diazomethane (2-4 equiv) and a low loading of Pd(OAc)(2) (<0.5 mol %). Diazoethane and diazobutane can also be employed and yield silyl cyclopropanes with diastereoselectivities of up to 10:1 for the trans isomer.

Highly beta-(E)-selective hydrosilylation of terminal and internal alkynes catalyzed by a (IPr)Pt(diene) complex.

The regioselective hydrosilylation of terminal and internal alkynes catalyzed by the novel (IPr)Pt(AE) ( 7) (IPr = bis(2,6-diisopropylphenyl)imidazo-2-ylidene, AE = allyl ether) complex is presented. The (IPr)Pt(AE) catalyst displays enhanced activity and regioselectivity for the hydrosilylation of terminal and internal alkynes with low catalyst loading (0.1 to 0.

Expanding the C2-symmetric bicyclo[2.2.1]hepta-2,5-diene ligand family: concise synthesis and catalytic activity in rhodium-catalyzed asymmetric addition.

New C2-symmetric bicyclo[2.2.1]hepta-2,5-dienes bearing methyl and phenyl substituents at the 2 and 5 positions were prepared enantiomerically pure through a two-step sequence starting from the readily available bicyclo[2.

Second generation N-heterocyclic carbene-Pt(0) complexes as efficient catalysts for the hydrosilylation of alkenes.

A new class of benzimidazolylidene carbene-Pt(0) complexes was developed and used to efficiently catalyse the hydrosilylation of alkenes.