Stepwise, multiple B-H bond activation is a major challenge in synthetic chemistry. Herein, we have developed a time-controlled method to monitor the process of B-H bond activation based on a...

Comprehensive Summary Herein, we describe the synthesis of a carborane‐supported octanuclear palladacycle complex, Pd8(o‐C2B10H10CS2CH3)4Cl4(CH3CN)4 (complex 1), with B(3)–H activations on o‐carborane ligand. The substitution reaction of 1 has been explored, and three of its substituted complexes Pd8(o‐C2B10H10CS2CH3)4Cl4(L)4 (L = tBuNC, 2; L = C5H5N, 3; L = C4H8S, 4) have been synthesized. The m‐ and p‐carborane disubstituted ligands m‐ and p‐C2B10H10(CS2CH3)2 (ligands 5 and 6) as well as their B—H activated carborane complexes [m‐C2B10H9(CS2CH3)2PdCl] (7) and [p‐C2B10H8(CS2CH3)2][PdCl(tBuNC)]2 (8) have also been synthesized by the similar method. All of these complexes have been characterized, including X‐ray single crystal diffraction, NMR spectroscopy, IR spectroscopy and elemental analysis methods.

Using methyldithiocarboxyl as the directing group, together with [Cp*IrCl2]2, selective B(3)–H activation occurs at o-carborane. A series of substitution complexes have been prepared from the B(3)–H activated complex.

The introduction of the 2-pyridylsulfenyl directing group to o-carboranes allowed either B(3)-Ir or B(4)-Ir bond formation using a steric effect strategy. Moreover, the reactivity of the B(4)-Rh o-carborane complexes with...