Coordination Chemistry and Organic Synthesis Utilizing Cycloalkane-1,2-dithiol

Abstract

An [OSSO]-type tetradentate ligand was prepared starting from trans-cyclooctane-1,2-dithiol. Hexacoordinated dibenzyl Zr complex was synthesized by the reaction of the ligand with Zr(CH₂Ph)₄ and its structure was fully characterized by nuclear magnetic resonance (NMR) spectroscopy and X-ray crystallography. The zirconium complex has the C₂ symmetry in solution. The zirconium complex activated with B(C₆F₅)₃ or (Ph₃C)[B(C₆F₅)₄] provided a highly active catalytic system for coordinate polymerization of 1-hexene to yield poly(1-hexene)s with high isospecificity.

Keywords:

• 1,2-Dithiol
• isospecificity
• polymerization
• trans-cyclooctanediyl
• zirconium

Acknowledgments

We thank Dr. Masayoshi Nishiura and Dr. Hou (Organometallic Chemistry Laboratory, RIKEN Advanced Science Institute) for their kind measurement of molecular weight and molecular weight distributions of poly(1-hexene)s by gel permeation chromatography. We are grateful to Dr. Kohei Tamao (RIKEN Advanced Science Institute) for his kind discussion.