Density Functional Theory Study of the d10Series (H3P)3M(η1-SO2) and (MenPh3-nP)3M(η1-SO2) (M = Ni, Pd, Pt;n= 0−3):  SO2Pyramidality and M−S Bond Dissociation Energies

Brust, Daniel J.; Gilbert, Thomas M.

doi:10.1021/ic030229q

Cited by 12 publications

(6 citation statements)

References 29 publications

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“…Although the energy decomposition gives some insight into the changes we observe in the reaction energies, there is not a single contribution that accounts for the observed trend in ∆E int . The values of ∆E orb and ∆E elstat , which in the literature are sometimes interpreted as the covalent and ionic contributions to the metal-ligand bond, both contribute to the interaction energy; 44,45 combined they account for the observed trend in ∆E int . The trend in the activation energy can only be related directly to the change in ∆E int .…”

Section: Resultsmentioning

confidence: 99%

Reductive Elimination of Organic Molecules from Palladium−Diphosphine Complexes

Zuidema

Leeuwen

2005

Organometallics

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The effects governing the rate of reductive elimination of dimethyl ether, acetonitrile, vinyl cyanide, and methyl ethanoate from palladium diphosphine complexes were studied by means of a density functional theory method. Energy barriers, computed as the difference in energy between the reactant and the corresponding transition state using H2P(CH2)2PH2 as model for diphosphine ligands, varied from 38 kcal mol-1 (dimethyl ether) to barrierless elimination of methyl ethanoate, in good agreement with experimental results. MO analysis reveals striking differences that are related to the donor/acceptor capabilities of the reacting moieties. For the elimination of acetonitrile, the bite angle effect on the reaction rate, observed by Moloy when different diphosphine ligands were used, was studied in depth. We considered (R2PXPR2)Pd(CH3)(CN) complexes for a number of different ligand backbones (X = (CH2) n , n = 1−4; X = cis-, trans-but-2-ene) which span a large bite angle range and for a number of different phosphine substituents (R = H, Me, Ph). With the use of QM/MM strategies, steric and electronic effects were separated and evaluated, and the results indicate that the rate enhancement is electronic in nature, steric effects being negligible. The analysis reveals that wide bite angle ligands destabilize the reactant and stabilize the transition state, thus accelerating the reaction.

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Section: Resultsmentioning

confidence: 99%

Reductive Elimination of Organic Molecules from Palladium−Diphosphine Complexes

Zuidema

Leeuwen

2005

Organometallics

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“…Releasing benzene or PhSMe from complex 16B occurs via TS 16B-17 or TS 16B-18A forming three-coordinated complex 17 or 18A (Fig. 7), followed by the corresponding reductive elimination through TS [17][18][19] COD ligand gives complex 21, and subsequently ligand substitution of Me 3 SiSMe with another COD regenerates complex Ni(COD) 2 1. Since the energy difference between TS 16B-17 and TS 16B-18A is only 0.5 kcal mol À1 , in order to give more accurate comparison, the single-point energies for these two transition states were re-calculated at the uB97XD/def2-QZVPPD level.…”

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confidence: 99%

Theoretical study on the reaction mechanism of “ligandless” Ni-catalyzed hydrodesulfurization of aryl sulfide

et al. 2017

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The reaction mechanism of Ni(COD) 2 catalyzed hydrodesulfurization of aryl sulfide PhSMe with HSiMe 3 as the reducing agent has been studied by using density functional theory methods. Both PhSMe-coordinated pathway and "ligandless" pathway have been identified and compared. It is found that these two reaction pathways are kinetically competitive and the s-complex assisted metathesis (s-CAM) transition state is the highest point on each energy profile for both pathways. Moreover, both the singlet and triplet reaction pathways of ligand substitutions have been compared and found that both singlet and triplet reaction mechanisms are competitive for the ligand substitution of COD with PhSMe on PhSMecoordinated pathway while the triplet mechanism holds a distinct advantage over singlet one for that of COD with HSiMe 3 on "ligandless" pathway.

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“…This last example (with ν CO = 2064, ν IrH = 1965 cm −1 ) and the PPh 3 analogue (ν CO = 2050, ν IrH = 1965 cm −1 ) are in some respects most akin to 1 and 2 and have been designated by Mingos as d 8 complexes; that is, the weak coordination of a Lewis acid to the metal center is not taken to constitute a two-electron oxidation or depletion in the d-configuration. In a similar manner Gilbert has recently reported a DFT study of the complexes [M(SO 2 )(PPh 3 ) 3 ] that describes these as having a d 10 configuration . Chart depicts compounds in support of this analogy.…”

Section: Resultsmentioning

confidence: 81%

Metallaboratranes: Bis- and Tris(methimazolyl)borane Complexes of Group 9 Metal Carbonyls and Thiocarbonyls

2009

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The iridium poly(methimazolyl)borane complexes [IrH(CE)(PPh3){κ3-B,S,S′-B(mt)2R}](Ir→B) 8 (mt = methimazolyl = 2-mercapto-3-methylimidazol-1-yl; E = O, S; R = mt, H) are described in detail. For R = mt, these materials are elucidated as paradigms for the final mechanistic intermediate in metallaboratrane formation, a role illustrated through hydride abstraction to afford the cationic salts [Ir(CE)(PPh3){κ4-B(mt)3}]X(Ir→B) 8 (E = O, S; X = Cl, BF4). The rhodium poly(methimazolyl)borate complexes [Rh(CO)(PPh3){κ2-S,S′-HB(mt)2R}] (R = mt, H) are also reported. These compounds are obtained in preference to the respective borane complexes (analogous to iridium); however [Rh(CO)(PPh3){κ2-S,S′-HB(mt)3}] is observed to undergo facile solution-phase conversion to [Rh(CO)(PPh3){κ4-B,S,S′,S′′-B(mt)3}]Cl(Rh→B) 8 in chlorinated solvents. The ramifications of these results, with respect to metallaboratrane formation, are discussed, substantiating previous mechanistic conjecture. In an attempt to establish an alternative route to iridaboratranes, the first isolable tris(methimazolyl)borate complex of iridium, cis,cis-[IrHCl(PPh3)2{κ2-S,S′-HB(mt)3], is reported and shown not to evolve to the iridaboratrane [IrCl(PPh3){κ4-B(mt)3}](Ir→B) 8 under conditions that lead to the corresponding rhodaboratrane. Factors are discussed that may contribute to this fine balance between the formation of methimazolylborate and methimazolylborane complexes.

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Density Functional Theory Study of the d¹⁰Series (H₃P)₃M(η¹-SO₂) and (Me_nPh₃_-_nP)₃M(η¹-SO₂) (M = Ni, Pd, Pt;n= 0−3): SO₂Pyramidality and M−S Bond Dissociation Energies

Cited by 12 publications

References 29 publications

Reductive Elimination of Organic Molecules from Palladium−Diphosphine Complexes

Reductive Elimination of Organic Molecules from Palladium−Diphosphine Complexes

Theoretical study on the reaction mechanism of “ligandless” Ni-catalyzed hydrodesulfurization of aryl sulfide

Metallaboratranes: Bis- and Tris(methimazolyl)borane Complexes of Group 9 Metal Carbonyls and Thiocarbonyls

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