Book Description

The work described herein focuses on the synthesis and characterization of new heterobimetallic complexes containing the redox-active W[SNS] 2 metalloligand and investigation into their electronic properties and reactivity. Most recent studies have explored the redox nature of the [SNS]H 3 scaffold through the synthesis and reactivity of a novel set of square-planar nickel complexes.Chapters 2 and 3 describe a modular synthetic approach towards generating a new series of heterobimetallic complexes with the general formula W[SNS]2M(L) ([SNS] = bis(2-mercapto- p-tolyl)amine; M = Ni, Pd, or Pt; and L = dppe, depe, dmpe, dppp, PR'2NRPR'2 (R = phenyl, benzyl; R'=phenyl), DPEphos or dppf). The complexes were prepared by a salt metathesis of Cl2MII(L) with the previously reported W[SNS]2 coordination complex under reducing conditions. X-ray diffraction analysis revealed interesting coordination geometries about the appended Group 10 metal centers moving from Pt and Pd (pseudo-square planar) to the first row Ni (pseudo-tetrahedral) analogue. These complexes demonstrate formal metal--metal bond formation across the series with a tunable first oxidation potential up to 600 mV.Chapter 4 investigates the use of W[SNS]2Ni(dppe) as a catalyst for the electrochemical reduction of protons to hydrogen. This complex was found to catalytically generate hydrogen with an overpotential of 700 mV, a TOF of 14 sec--1, and a Faradaic yield of 80 +/- 3 % using 4-cyanoanilinium tetrafluoroborate in non-aqueous solutions.Chapter 5 demonstrates the effect of exchanging the nickel center of the heterobimetallic complexes discussed in Chapters 2 and 3 with other first row transitions metal ions (i.e. cobalt and copper). Analysis into the observed metal--metal distances reveal stark differences across the series. Additionally, the copper ion containing complexes demonstrate dynamic behavior in solution.Chapter 6 investigates the synthesis and reactivity of a series of monomeric square-planar nickel complexes of the [SNS] scaffold to demonstrate the ligand as redox, proton, and hydrogen atom non-innocent.Appendix A illustrates the electrochemical responses observed for the monoanionic complexes from Chapter 6 in the presence of CO2 and CO. Appendices B and C describe the synthesis and characterization of a five-coordinate cobalt and a heterotrimetallic tungsten-nickel complex, respectively.