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Title:Mixed-valence bimetallic dithiolates of iron, cobalt, and nickel and their relevance to the hydrogenases
Author(s):Chambers, Geoffrey M
Director of Research:Rauchfuss, Thomas B
Doctoral Committee Chair(s):Rauchfuss, Thomas B
Doctoral Committee Member(s):Girolami, Gregory S; Fout, Alison R; Vura-Weis, Josh
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):hydrogenase
model compounds
mixed-valence
mixed-valent
proton reduction
HER
Ni-L
Ni-SIa
Ni-C
CpNi
nickelocene
thiols
thiol
thiolate
thiolates
flippamer
flippamers
dithiolate
dithiol
Abstract:The world's energy economy is driven by petroleum, but this resource is limited and its consumption drives global climate change. As a result, it is crucial for the ongoing prosperity of humans to find an alternative means of energy production and storage. One alternative is hydrogen. Nature utilizes metalloproteins called hydrogenases (H2ases) to efficiently interconvert protons and electrons with dihydrogen. Though this is one of the simplest possible reactions, it is of utmost importance for countless microorganisms. The performance of these enzymes exceeds that of the leading artificial catalyst used by humans: platinum. Though platinum based catalysts are currently the best, the scarcity of this metal makes widespread utilization unfeasible. Nature, by necessity, must utilize earth abundant metals. Indeed, the premier enzymes that facilitate this reaction utilize the abundant metals nickel and iron. The active sites the [NiFe]- and [FeFe]-H2ases possess bimetallic cores bridged by thiolates. The iron centers are ligated by species that are peculiar in biological systems: carbon monoxide and cyanide. Due to the effectiveness of H2ases as H2 oxidation proton reduction catalysts, there is a strong drive to synthesize small molecule models of these active sites. Chapter 1 introduces hydrogen in the context of energy storage and microbiology and continues on to describe the details of the hydrogenases. The second half of this chapter discuses model compounds of the hydrogenases and various strategies, challenges, and successes in this area. Though more is known about the [NiFe]-H2ase, model compounds to date have largely failed to replicate any of the extensive mixed-valent states of this active site. This thesis advances this area specifically through the synthesis and examination of mixed-valent bimetallic dithiolate complexes. Chapter 2 focuses on the NiRu dithiolate compound (dppe)Ni(pdt)Ru(pcymene)(dppe = 1,2-bis(diphenylphosphino)ethane; pdt = 1,3-propanedithiolate, p-cymene =p-isopropyltoluene). The protonation and oxidation chemistry of this system are described. The principal finding this work is that the mixed-valent cation [(dppe)Ni(pdt)Ru(p-cymene)]+ both structurally and spectroscopically mimics the [NiFe]-H2ase active site in the Ni-L state and is the first such reported example. A disadvantage of these compounds is that they contain the platinum-group metal ruthenium. All other chapters in this thesis utilize only first row transition metals. Chapter 3 discusses the synthesis and properties of the cyclopentadienyl NiFe compound [CpNi(pdt)Fe(dppe)CO]BF4 (Cp = cyclopentadienide). These cyclopentadienyl complexes are the first reported examples of model compounds to accurately replicate theredox inactive iron center of [NiFe]-H2ase. Additionally, this system is shown to stabilize nickel in the first, second, and third oxidation states. Treatment of the Ni(II)Fe(II) compound [CpNi(pdt)Fe(dppe)CO]BF4 affords the neutral, mixed-valent compound CpNi(pdt)Fe(dppe)CO, which has been extensively characterized through numerous spectroscopic techniques and DFT calculations to be a bona fide Ni(I)Fe(II) complex. When this compound is treated with acid, the Ni(II)Fe(II) cation [CpNi(pdt)Fe(dppe)CO]+ is regenerated with the concomitant production of 0.5 equiv. of H2 making this system a proton reduction catalyst. The catalytic cycle was analyzed using DFT. The mixed-valence hydride [CpNi(pdt)(μ-H)Fe(dppe)CO]BF4 is not observed directly but is unambiguously Ni(III)Fe(II), akin to the mixed-valent Ni-C state of [NiFe]-H2ase, by DFT analysis. Chapter 4 describes the synthesis and characterization of mixed-valent di- and tri-nickel cyclopentadienyl dithiolates. The reaction between nickelocene and monothiols has long been known to yield dimers of the form [CpNi(SR)]2 with loss of CpH. The reaction of nickelocene with dithiols is investigated in chapter 4 and is found to be quite complex: dinickel, trinickel, and pentanickel species are formed. In contrast to the known monothiolate dimers, the dithiolate compounds feature a pyramidalized Ni2S2 core by virtue of the dithiolate linker. This distortion of the Ni2S2 core forces the two nickel centers together. As a consequence, the dinickel compounds Cp2Ni2(pdt) and Cp2Ni2(edt) (edt = 1,2-ethanedithiolate) have a thermally accessible triplet state, a feature which has been proposed in some DFT analyses of the [NiFe]-H2ase active site. Another consequence of the close proximity of these metal centers is a facile one electron oxidation to generate Ni(2.5)2 compounds. This chapter includes DFT analysis of the monothiolate dimer Cp2Ni2(SEt)2 in which the Ni2S2 core is distorted computationally. This study shows the drastic effects of bending the Ni2S2 core. Chapter 5 investigates the properties of the mixed-valent cation [Cp2Co2(pdt)]+ and the mixed-valent bridging hydride complexes Cp2Co2(xdt)H (xdt = edt, pdt). The CpCo fragment is isoelectronic with the Fe(CO)3 fragment that frequently appears in model complexes. The cation [Cp2Co2(pdt)]+ generates the bridging hydroxide cation[Cp2Co2(pdt)OH]+ upon treatment with aqueous THF. Similarly, the bridging thiolates compounds are generated upon treatment of [Cp2Co2(pdt)]+ with thiols. Both the mixed-valent bridging hydride compounds and the mixed-valent cation are discrete Co(III)Co(II) species, in contrast to the Ni(2.5)2 species in the analogous nickel systems.
Issue Date:2016-01-21
Type:Thesis
URI:http://hdl.handle.net/2142/90710
Rights Information:Copyright 2016 Geoffrey M. Chambers
Date Available in IDEALS:2016-07-07
Date Deposited:2016-05


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