Regioselective B(3)–H bond activation based on ano-carboranyl dithiocarboxylate ligand and its derivatives

Abstract

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.

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

“…The average length of B—Pd bonds is 203.4 pm, which is comparable to previous reported 204.4 pm. [ 17 ] However, the C=S "double" bond length increases from 162.6 pm on the free ligand [ 14 ] to 175.7 pm on complex 1 , which can be considered as an increasing single bond character and hence suggests a strong influence from the side bonded palladium atom. The (S=)C—Pd bonds have a length of 206.9 pm and the (C=)S—Pd bonds are 226.3 pm, which are close to the sum of elements' covalent radii and can be compared to previous work, [ 13,17 ] thus it can be speculated that the bonding between central side‐on coordinated palladium atoms and methyldithiocarboxyl group is more close to "cyclopropane" motif with Pd—C and Pd—S single bonds than a common π‐complex motif.…”

“…The starting material PdCl 2 (CH 3 CN) 2 was prepared by refluxing anhydrous PdCl 2 with CH 3 CN and o ‐C 2 B 10 H 11 CS 2 CH 3 was prepared by literature method. [ 14 ] 1 H, 13 C and 11 B NMR spectra were recorded on Bruker AVANCE III HD 400 MHz spectrometer or Bruker AVANCE III HD 500 MHz spectrometer. Spectra were recorded at room temperature and referenced to the residual protonated solvent for NMR spectra.…”

“…As shown in our previous work, methyldithiocarboxyl group can induce B(3)–H activation of o ‐carborane with the formation of boron‐iridated complex efficiently. [ 14 ] Because of the soft acid property of Pd II centre and the soft base property of sulfur atom, it can be speculated that there are the probable interaction between methyldithiocarboxyl group and Pd II centre and further Pd‐induced B—H activation. In this work, Pd(CH 3 CN) 2 Cl 2 which contains two easily‐dissociated acetonitrile ligands has been selected to investigate the possibility of Pd‐induced regioselective B—H activation.…”

Supramolecular Architectures Bearing Half-Sandwich Iridium- or Rhodium-Based Carboranes: Design, Synthesis, and Applications

“…In the crystal structure of complex 8, the hydrogen atoms bound to B(1) and B(10) (that is, two five-coordinate boron vertices) in [B 10 H 10 ] 2− interact with the Ir corner, which is likely owing to the charge distribution of the cluster (Figure 3). 37 Figure 1. Structures of " [12]mercuracarborand-4" and its binding to halogen anions.…”