Molybdenum Carbonyl Complexes with a Polymerizable Phosphorus/Nitrogen/Phosphorus Ligand and Corresponding Conducting Metallopolymers

Abstract

The design, synthesis, and characterization of the novel polymerizable ligand 3,5‐bis(3,4‐ethylenedioxythien‐2‐yl)‐N,N‐bis(2‐diphenylphosphinoethyl)‐phenylamine is achieved. The corresponding molybdenum complexes (EDOT)2PNP‐Mo(CO) n where n = 3,4 with carbonyls as ancillary ligands are also synthesized, and characterized by 1H NMR, 31P{1H} NMR, HRMS, FTIR (both the solution state spectrum between KBr discs and the solid‐state spectrum with attenuated total reflectance [ATR] apparatus). Single crystal X‐ray analysis of (EDOT)2PNP‐Mo(CO)3 complex is performed. The monomer complexes and the free ligand are electropolymerized to obtain the corresponding polymers that are studied electrochemically. The Mo/P and Mo/S ratios as well as the metal oxidations in the conducting metallopolymers are analyzed by X‐ray photoelectron spectroscopy.