Platinum-catalyzed C-H arylation of simple arenes.

This report describes the Na2PtCl4 catalyzed C-H arylation of arene substrates with diaryliodonium salts. The site selectivity of these reactions is predominantly controlled by steric factors. Remarkably, Na2PtCl4-catalyzed naphthalene arylation proceeds with opposite site selectivity compared to that obtained with Na2PdCl4 as the catalyst. Preliminary mechanistic studies provide evidence for a Pt(II)/Pt(IV) catalytic cycle involving rate-limiting C-C bond-forming reductive elimination.

High-valent organometallic copper and palladium in catalysis.

Copper and palladium catalysts are critically important in numerous commercial chemical processes. Improvements in the activity, selectivity and scope of these catalysts could drastically reduce the environmental impact, and increase the sustainability, of chemical reactions. One rapidly developing strategy for achieving these goals is to use 'high-valent' organometallic copper and palladium intermediates in catalysis. Here we describe recent advances involving both the fundamental chemistry and the applications of these high-valent metal complexes in numerous synthetically useful catalytic transformations.

Highly dispersed palladium(II) in a defective metal-organic framework: application to C-H activation and functionalization.

High reversibility during crystallization leads to relatively defect-free crystals through repair of nonperiodic inclusions, including those derived from impurities. Microporous coordination polymers (MCPs) can achieve a high level of crystallinity through a related mechanism whereby coordination defects are repaired, leading to single crystals. In this work, we discovered and exploited the fact that this process is far from perfect for MCPs and that a minority ligand that is coordinatively identical to but distinct in shape from the majority linker can be inserted into the framework, resulting in defects. The reaction of Zn(II) with 1,4-benzenedicarboxylic acid (H(2)BDC) in the presence of small amounts of 1,3,5-tris(4-carboxyphenyl)benzene (H(3)BTB) leads to a new crystalline material, MOF-5(O(h)), that is nearly identical to MOF-5 but has an octahedral morphology and a number of defect sites that are uniquely functionalized with dangling carboxylates. The reaction with Pd(OAc)(2) impregnates the metal ions, creating a heterogeneous catalyst with ultrahigh surface area. The Pd(II)-catalyzed phenylation of naphthalene within Pd-impregnated MOF-5(O(h)) demonstrates the potential utility of an MCP framework for modulating the reactivity and selectivity of such transformations. Furthermore, this novel synthetic approach can be applied to different MCPs and will provide scaffolds functionalized with catalytically active metal species.