Steric strains (F-strain or front-strain) in the acid-base interaction between the Lewis acid [TpMe2Ir(C6H5)2] and 2-substituted pyridines Lewis bases, are responsible for the stabilization of the C-adducts (2) of the respective pyridine carbene tautomers over the expected N-adducts.

Contents:-General.-Synthesis and spectroscopic and analytical data for new compounds.-Table S.1. Crystal data and structure refinement for compound 3.

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The Ir(III) compound Tp(Ms'')Ir(N2), that contains a pentadentate, doubly metalated 3-mesityl substituted tris(pyrazolyl)borate ligand, induces the cleavage of C-H and C-Cl bonds of CH2Cl2 to yield a highly electrophilic chlorocarbene Ir=C(H)Cl complex.

C-Br bond activation followed by a C-C coupling reaction of the 2-bromo-pyridyl unit of [1-phenyl-2-(6-bromopyridin-2-yl)-benzoimidazole] was performed by Pd(CH(2)CMe(2)-o-C(6)H(4))(η(4)-COD). Two new seven membered palladacycles were obtained. A combined experimental and theoretical DFT study elucidates the mechanism for this reaction.

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A small library of seven-membered palladacycles and asymmetric bipyridines was prepared via C–Br activation and C–C coupling reactions.

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