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Redox non-innocent metal dithiolene or diamine complexes are potential alternative catalysts in hydrogen evolution reaction and have been incorporated into 2D metal–organic frameworks to obtain une...

Described herein is a comparative theoretical study of dehydrogenative C(sp)-H functionalizations of a terminal alkyne with group-14-based hydrides (HEEt3; E = Si, Ge, Sn) catalyzed by an Ohki-Tatsumi complex-a cationic Ru(II) complex with a tethered thiolate ligand ([Ru-S] = [(DmpS)Ru(PiPr3)][BAr4F]; Dmp = 2,6-(dimesityl)2C6H3; ArF = 3,5-(CF3)2C6H3). The calculations indicate that the energy barriers for heterolytic cleavage of the H-EEt3 bonds at the Ru-S sites of the Ohki-Tatsumi complex highly vary depending on the group 14 elements from 3.8 kcal/mol (E = Sn) to 10.5 kcal/mol (E = Ge) and 18.5 kcal/mol (E = Si), where Ru and S elements cooperatively serve as the Lewis acid and base, respectively. Likewise, the transfer of the group 14 cation (Et3E+) to the C-C triple bond to generate the β-element-stabilized vinyl cations-the rate-determining step (RDS) of the overall reaction-is predicted to be susceptible to the element's identity [Ea = 36.8 for Sn < 42.9 and Ge < 50.7 for Si (kcal/mol)]. The key transition states involved in the RDS are compared in terms of energy and structure within each system of the group 14 hydrides. The distortion/interaction-activation strain (DIAS) model analysis of the transition states responsible for dehydrogenative stannylation and hydrostannation of a terminal alkyne sheds light on the origin of the experimentally observed kinetic preference toward dehydrogenative C-H stannylation over hydrostannation.

Platinum bis(dithiolene) complexes have reactivity toward alkenes like nickel bis(dithiolene) complexes. We examined the uptake of 1,3-butadiene by platinum bis(dithiolene) [Pt(tfd)2] (tfd = S2C2(CF3)2) via a density functional theory study; both 1,2- and 1,4-additions of 1,3-butadiene to the ligands of Pt(tfd)2 to form both interligand and intraligand adducts were studied. For single 1,3-butadiene addition, direct 1,4-addition on interligand S-S, 1,2-addition on intraligand S-S, and 1,4-addition on intraligand S-C are all feasible at room temperature and are controlled by the symmetry of the highest occupied molecular orbital of 1,3-butadiene and the lowest unoccupied molecular orbital of Pt(tfd)2. However, the formation of the interligand S-S adduct through 1,4-addition of one molecule of cis-1,3-butadiene is the most favorable route, with a reaction barrier of 9.3 kcal/mol. The other two addition processes cannot compete with this one due to both higher reaction barriers and unstable adducts. Other possible pathways, such as formation of cis-interligand S-S adduct from 1,2-addition of one molecule of 1,3-butadiene via a twisted trans-interligand S-S adduct, have higher barriers. Our calculated results show that 1,4-addition of a single molecule of 1,3-butadiene on the interligand S-S gives the kinetically stable product by a one-step pathway. But of at least equal importance is the apofacial 1,4-addition of two molecules of 1,3-butadiene on the intraligand S-C of the same ligand on Pt(tfd)2, which yields the thermodynamically stable product, obtained via a short lifetime intermediate, the 1:1 intraligand S-C adduct, being formed through several pathways. The calculated results in this study well explain the experimental observation that 1:1 interligand S-S adduct was formed in a short time, and the intraligand S-C adduct from two molecules of cis-1,3-butadiene was accumulated in 20 h at 50° and characterized by X-ray crystallography.

Nickel dithiolene complexes have been proposed as electrocatalysts for alkene purification. Recent studies of the ligand-based reactions of Ni(tfd)2 (tfd = S2C2(CF3)2) and its anion [Ni(tfd)2](-) with alkenes (ethylene and 1-hexene) showed that in the absence of the anion, the reaction proceeds most rapidly to form the intraligand adduct, which decomposes by releasing a substituted dihydrodithiin. However, the presence of the anion increases the rate of formation of the stable cis-interligand adduct, and decreases the rate of dihydrodithiin formation and decomposition. In spite of both computational and experimental studies, the mechanism, especially the role of the anion, remained somewhat elusive. We are now providing a combined experimental and computational study that addresses the mechanism and explains the role of the anion. A kinetic study (global analysis) for the reaction of 1-hexene is reported, which supports the following mechanism: (1) reversible intraligand addition, (2) oxidation of the intraligand addition product prior to decomposition, and (3) interligand adduct formation catalyzed by Ni(tfd)2(-). Density functional theory (DFT) calculations were performed on the Ni(tfd)2/Ni(tfd)2(-)/ethylene system to shed light on the selectivity of adduct formation in the absence of anion and on the mechanism in which Ni(tfd)2(-) shifts the reaction from intraligand addition to interligand addition. Computational results show that in the neutral system the free energy of activation for intraligand addition is lower than that for interligand addition, in agreement with the experimental results. The computations predict that the anion enhances the rate of the cis-interligand adduct formation by forming a dimetallic complex with the neutral complex. The [(Ni(tfd)2)2](-) dimetallic complex then coordinates ethylene and isomerizes to form a Ni,S-bound ethylene complex, which then rapidly isomerizes to the stable interligand adduct but not to the intraligand adduct. Thus, the anion catalyzes the formation of the interligand adduct. Significant experimental evidence for dimetallic species derived from nickel bis(dithiolene) complexes has been found. ESI-MS data indicate the presence of a [(Ni(tfd)2)2](-) dimetallic complex as the acetonitrile adduct. A charge-neutral association complex of Ni(tfd)2 with the ethylene adduct of Ni(tfd)2 has been crystallographically characterized. Despite the small driving force for the reversible association, very major structural reorganization (square-planar → octahedral) occurs.