Octanuclear Palladacycles with B(3)–H Bond Activation of o‐Carborane†

Comprehensive Summary Herein, we describe the synthesis of a carborane‐supported octanuclear palladacycle complex, Pd 8 ( o ‐C 2 B 10 H 10 CS 2 CH 3 ) 4 Cl 4 (CH 3 CN) 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 Pd 8 ( o ‐C 2 B 10 H 10 CS 2 CH 3 ) 4 Cl 4 (L) 4 (L = t BuNC, 2 ; L = C 5 H 5 N, 3 ; L = C 4 H 8 S, 4 ) have been synthesized. The m ‐ and p ‐carborane disubstituted ligands m ‐ and p ‐C 2 B 10 H 10 (CS 2 CH 3 ) 2 (ligands 5 and 6 ) as well as their B—H activated carborane complexes [ m ‐C 2 B 10 H 9 (CS 2 CH 3 ) 2 PdCl] ( 7 ) and [ p ‐C 2 B 10 H 8 (CS 2 CH 3 ) 2 ][PdCl( t BuNC)] 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.