2004
DOI: 10.1021/ic030229q
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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

Abstract: Quantum mechanical density functional theory (DFT) and coupled DFT/molecular mechanics (QMMM) studies of the compounds (H(3)P)(3)M(eta(1)-SO(2)) and (Me(n)Ph(3-n)P)(3)M(eta(1)-SO(2)) (M = Ni, Pd, Pt; n = 0-3) model the experimental data well, particularly the planar/pyramidal geometries at sulfur. Bond dissociation energy (BDE) calculations confirm that Pd/Pt systems with pyramidal SO(2) ligands exhibit M-S BDEs smaller by 30-50% than Ni systems with planar SO(2). However, scans of the potential energy surface… Show more

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Cited by 12 publications
(6 citation statements)
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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%
“…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%
“…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.…”
mentioning
confidence: 99%
“…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%