Charge distribution and nucleophilic reactivity in sulfur ligand chelates. Dialkyl derivatives of nickel(II), palladium(II), and platinum(II) bis(cis ethylenedithiolates)

Schrauzer, G. N.; Rabinowitz, H. N.

doi:10.1021/ja01018a019

Cited by 76 publications

(25 citation statements)

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“…Several papers demonstrated that the metal bis (dithiolene) complexes display high reactivity toward strained and cyclic alkenes, forming cyclo-addition products [6,[8][9][10][11][12][13][14][15][16][17][18][19]. However, a direct pathway that leads to the formation of the desired cisinterligand adduct is symmetry-forbidden, which is in line with the Woodward-Hoffman addition rules [20].…”

Section: Introductionmentioning

confidence: 93%

Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification

et al. 2020

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Considering that olefins present a large volume feedstock, it is reasonable to expect that their purification is industrially critical. After the discovery of the nickel bis (dithiolene) complex Ni(S 2 C 2 (CF 3) 2) 2 that exhibits electro-catalytic activity with olefins but tends to decompose by a competitive reaction route, related complexes have been explored experimentally and theoretically. In this paper, a computational examination is performed on differently charged cobalt and copper bis (oxothiolene) complexes [M (OSC 2 (CN) 2) 2 ] to test their potential applicability as the catalysts for olefin purification, using the simplest olefin, ethylene. Possible reaction pathways for ethylene addition on these complexes were explored, to determine whether some of these candidates can avoid the reaction route that leads to decomposition, which is distinctive from the nickel complex, and to form stable adducts that can subsequently release ethylene by reduction. Our calculations suggest that the neutral cobalt complex might be an alternative catalyst, because all its forms can bind ethylene to produce stable interligand adducts with moderate to low activation barriers, rather than to form intraligand adducts that lead to decomposition. The calculations also predict that these interligand adducts are capable of releasing ethylene upon reduction. In addition, it can produce the desired interligand adducts following two different reaction pathways, assigned as the direct and the indirect, with no need for anion species as co-catalysts, which is crucial for the nickel complex. Thus, the olefin purification process could be much simpler by using this catalyst.

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Section: Introductionmentioning

confidence: 93%

Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification

et al. 2020

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“…They also discovered that the dithiolene complexes are not poisoned by hydrogen, carbon monoxide, acetylene or hydrogen sulfide, which are commonly present in olefin streams, presumably because olefin binding occurs through the sulfur ligand rather than the metal center. In addition, Schrauzer et al reported that M(S 2 C 2 Ph 2 ) 2 (M = Ni, Pd, Pt; Ph = Phenyl group) reacts with norbornadiene (Schrauzer & Mayweg, 1965;Schrauzer & Rabinowitz, 1968;Schrauzer et al, 1970), and Wing et al also proposed that Ni[S 2 C 2 (CF 3 ) 2 ] 2 reacts with norbornadiene and 2,3-dimethyl-1,3-butadiene to form 1/1 olefin adducts (Wing et al, 1970), where the olefin binds to ligand S atoms rather than the metal. Theoretical studies on the reaction of ethylene and Ni(S 2 C 2 R 2 ) 2 (R = H, CN, CF 3 ) in gas phase were performed by Fan et al.…”

Section: Introductionmentioning

confidence: 99%

Estimation of Solvent Effects for the Complexing Reaction of Propylene and Nickel Dithiolene

2007

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The formation of olefin complexes is of potential importance in the separation of olefins. The solvents affect the activation energies, and hence the rates and equilibrium constants of the complexing reactions, which performance should be well estimated for the purpose of industrial practice. The solvent effects on the complexing reaction of propylene and nickel dithiolene Ni(S 2 C 2 H 2) 2 + C 2 H 4 =CH 2 → Ni(S 2 C 2 H 2) 2 ⋅C 2 H 4 =CH 2 are studied in this work, using density functional theory with B3LYP and an Onsager model. Complete optimizations of all the stagnation points are performed in benzene, toluene, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, acetone, ethanol, methanol, 1,2,3-propanetriol, dimethylsulfoxide and water, respectively. The reaction of complexing nickel dithiolene with propylene is a two-step process: the first step coordinates the propylene to S atoms in dithiolene, forming a trans-structural intermediate. The second step then yields the cis-structural product. The activation energy of the first step is higher than that of the second, indicating that the first step is the rate-determining step. The solvents make slight changes in the geometries of the reactants, transition states, intermediates and products. However, the corresponding molecular dipole moment becomes large with increase of the solvent polarity, which is beneficial to accelerate the reaction. Furthermore, the activation energies of the first (or second) step will exponentially decrease from 125.0 to 113.0 kJ⋅mol −1 (or from 101.8 to 83.43 kJ⋅mol −1) when the dielectric constants of solvents increase from 1.00 to 78.39, while the reaction rates of the first (or second) step exponentially increase from 0.7673×10-9 to 96.20×10-9 ⋅s −1

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“…It has been known that the square planar bis (1,2-diphenyl-1,2-ethenedithiolato)metal complexes (metal ¼ Ni, Pd, and Pt) form 1:1 adducts with dienes, such as norbornadiene (NBD) [10] and 2,3-dimethyl-1,3-butadiene [11], and with strained molecules, such as quadricyclane (Eq. (1)) [12].…”

Section: Introductionmentioning

confidence: 99%

Formation, structure, and reactivities of 1:1 adducts between quadricyclane and (η5-cyclopentadienyl)(1,2-diphenyl- or -dimethoxycarbonyl-1,2-ethenedithiolato)rhodium(III)

Nomura

Hatano

Fujita

et al. 2004

Journal of Organometallic Chemistry

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Charge distribution and nucleophilic reactivity in sulfur ligand chelates. Dialkyl derivatives of nickel(II), palladium(II), and platinum(II) bis(cis ethylenedithiolates)

Cited by 76 publications

References 0 publications

Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification

Computational investigation of cobalt and copper bis (oxothiolene) complexes as an alternative for olefin purification

Estimation of Solvent Effects for the Complexing Reaction of Propylene and Nickel Dithiolene

Formation, structure, and reactivities of 1:1 adducts between quadricyclane and (η5-cyclopentadienyl)(1,2-diphenyl- or -dimethoxycarbonyl-1,2-ethenedithiolato)rhodium(III)

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