Louise A. Berben's research while affiliated with University of California, Davis and other places

... 28,29 In practice, reduction of D + is oen coupled with proton transfer (PT) reactions and then the CV waveform manifests as an irreversible redox event where both thermodynamic and kinetic contributions to the D +/0 and D 0/ − redox couples and PT inuence the necessary applied potential (E p ) that is required to generate D-H. 30 Metal ion coordination is known qualitatively to lower E p for organic molecules including DHP − s but not enough data has been reported to draw any correlations between structure and function. 31,32 In this report, we investigate structural tuning of dihydropyridinates (DHP − ) and their precursors via metal ion effects. ...

... According to the literature, [23] imidazolium-based ionic liquids have been recognized as efficient supporting electrolytes and as effective promoters for CO 2 activation, contributing to the acceleration of the electrocatalytic activity of the eCO 2 RR and the generation of diverse valuable products. Furthermore, the electrolyte composition is also a critical factor influencing the eCO 2 RR. ...

... [13][14][15] More recently, the Berben group has utilized pre-equilibrium hydride formation with their iron cluster catalyst systems to increase the kinetics of hydride transfer while simultaneously lowering overpotential. 16 While promising, these approaches have limited applicability. Currently, there are no reported methods that can be used for non-cluster complexes that proceed via "inner-sphere" or concerted hydride transfer pathways. ...

... 22 Reactive CO2 capture utilises captured CO2 directly as the substrate, making these processes more economically viable. 23 Amines can capture CO2 as carbamates, and their presence in the coordination spheres of catalysts can alter the reactivity 24 and selectivity [25][26][27] of electrocatalytic CO2RR. Photocatalytic carbamate or carbonate reduction has not been reported. ...

... Transition metal complexes that incorporate group 15 elements have attracted increasing interest in the past three decades mainly due to their unprecedented structures [1] and flexible coordination behaviors, which render them versatile building blocks in supramolecular chemistry [1][2][3][4]. Within this field, cobalt clusters containing phosphorus and arsenic atoms have emerged as active materials for catalysis [5][6][7], magnetism [8], and as potential precursors for CoP nanoparticles [9]. In 1969, the Dahl group reported the first examples in this field, which included the tetrahedral arsenic-cobalt carbonyl clusters As3{Co(CO)3} and As2{Co(CO)3}2 obtained from the reaction of Co2(CO)8 with [AsCH3]5 and AsCl3, respectively [10,11]. ...

... The multiple metal−metal bonds in the clusters serve as multiple sites for protonation, and this should provide a kinetic boost to the rate of cluster-hydride formation. 30,31 In addition, the high anionic charges, 3− or 4−, on the clusters promote PT: while the delocalized structures of the clusters enable access to modest reduction potentials relative to single-metal site electrocatalysts, at a given formal oxidation state or overall charge. 32 A remaining challenge is to design a complete catalytic cycle competent for solar fuel chemistry or chemical synthesis which has fast hydride formation without H 2 production. ...

... 6,7 The molecular nature of these clusters allows us to gain detailed structural insight into the electrocatalytic active species and into the overall mechanism occurring in the catalyst microenvironment. 8 In this sense, the study of larger and larger molecular clusters such as HNMCCs represents an exciting frontier that could create a bridge to contemporary nanomaterials for electronic and electrochemical applications. 9−13 The redox behavior of HNMCCs has been investigated by electrochemical and spectroelectrochemical methods, and recently, we reported the first two cases of multivalence in large Ni−Pd molecular nanoclusters. ...

... As an example, using the direct HT approach, selectivity for the 1,3-DHPisomer of a tridentate diiminepyridine (I 2 P) ligand was demonstrated (Scheme 5 bottom). 89 The identity of the metal in a metal hydride can also influence the regioselectivity of hydride addition. Comparison of Mg to calcium (Ca) reagents indicates that the larger ionic size of Ca favoured the formation of the M-(1,2-DHP -) complex while the smaller Mg ion gave both 1,2-and 1,4-DHPproducts. ...

... The exciting electronic structure and the physicochemical and catalytic properties exerted by redox-active pincer ligands (such as L 1 ) with alkali, transition or main group metal ions are very interesting and an active area of research. [1][2][3][4][5][6][7][8] The reduction of NNN-type pincer ligands by more than two electrons is an extremely challenging task, as evidenced by the limited number of such complexes reported to date. [9][10][11][12][13] Developing a synthetic strategy and stabilising such magnificent molecules are of wide interest for activating small, thermodynamically stable molecules such as H 2 , N 2 , CO 2 , etc., to utilise them as commodity chemicals, as well as other targeted catalytic activities. ...

... For 2 + we know that the anking pyrazolyl rings of pz 2 P have N-donor atoms oriented in toward the cationic N-Me-pyridyl group, and in 2H those N-donor atoms of the pyrazolyl rings rotate away since the py ring is no longer cationic, as in the known structure of pz 2 P where the pyrazolyl N atoms rotate out. 36 An additional effect of the Group 13 cation may be to stabilize the DHP − via bonding interactions between the N py p-electrons and p z orbital of the metal: electron donation from N py to group 13 3+ cations have been observed in other complexes of tridentate pyridyl-centered ligands, 49 and may stabilize the DHP − . 50 ...