The influence of aryl ligands on the chemical hardness of triarylitin cations

Kravtsov, D. N.; Peregudov, Аlexander S.; Pachevskaya, V. M.; Golovchenko, L. S.

doi:10.1016/s0022-328x(96)06758-7

Cited by 3 publications

(3 citation statements)

References 14 publications

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“…The methodology of group electronegativity, hardness, and softness can indeed be applied to tin compounds without any fundamental changes, as relativistic effects may still be expected to be relatively small and probably are canceled out in the evaluation of these quantities which is no longer the case for fifth and higher row elements. Peregudov and his group have done studies on this kind of compound, [44][45][46][47][48][49] their approach being, however, less in line with our previous contributions and concentrating on large groups.…”

Section: Introductionmentioning

confidence: 99%

DFT Calculations of ¹¹⁹Sn Chemical Shifts Using Gauge-Including Atomic Orbitals and Their Interpretation via Group Properties

et al. 2002

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Nonrelativistic DFT calculations of the 119 Sn chemical shift are presented for a large series of tetracoordinated Sn compounds, of the type CH 3 SnRR′R′′, where R, R′, R′′ are halogens, alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The B3PW91 functional is used in conjunction with the IGLO III basis set. Leaving out compounds associating in solution and thus changing the Sn coordination, a correlation coefficient r 2 of 0.978 ( 0.023 is obtained between solvent NMR shifts and calculated values, with a slope of 0.984. These results indicate that this methodology yields excellent results both in the absolute and relative sense for the majority of the cases studied, where cancellation of errors (solvent and relativistic effects) occurs. The results were interpreted in terms of calculated electronegativity, hardness, and softness of the groups SnRR′R′′, applying a methodology previously developed by us (J. Phys. Chem. 1993, 97, 1826) and using the 6-311++G** basis set for H, C, Cl, Br, O, and S and 3-21G for Sn and I. Sequences of group electronegativities and hardnesses could be rationalized via previously calculated or experimental first and second row atomic or functional group values reflecting the interplay of qualitative and quantitative changes in groups on the central Sn atom. The evolution of the 119 Sn chemical shift can be successfully interpreted on the basis of group electronegativities for groups introduced in the β position of the Sn atom, whereas changes in R position (i.e., groups directly bonded to Sn) turn out to be essentially hardness related, especially when changes in the row of the periodic table are involved.

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Section: Introductionmentioning

confidence: 99%

DFT Calculations of ¹¹⁹Sn Chemical Shifts Using Gauge-Including Atomic Orbitals and Their Interpretation via Group Properties

et al. 2002

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“…In spite of computational advances and the availability of large number of experimental data [13,14], no many theoretical studies have been reported for group electronegativities, hardness and softness on molecules that contain atoms of the fourth group [15][16][17]. Peregudov and his group have done studies on this kind of compounds [18][19][20][21][22], finding some good correlation between experimental and theoretical values of the electronegativity and experimental 19 F NMR spectroscopy data.…”

Section: Introductionmentioning

confidence: 99%

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Vivas‐Reyes

Aria

2008

Eclet. Quím.

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Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH 3 SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119 Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH 3 , H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

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“…This fact suggests that from isoelectronegative Ar 3 Sn and Ar 3 Pb groups the tin-containing groups are much harder than lead-containing ones.We have also studied reactions in systems involving the softer Ph 3 Pb and the harder Ph 3 Sn groups. This fact is the basis for study of quantitative regularities in the influence of sor n-ligands on the hardness of ArHg, Ar 3 Sn and Ar 3 PAu cations in the reactions[20]-[22]:85,86,90 If Q * , X and Y are constants and Q equals L n M, we obtain the final expression:log K eq a L n M c Thus we can formulate the general conclusion that the influence of the ligand L on log K eq will reflect its influence on the chemical hardness of the L n M + cation.…”

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Electronegativity and chemical hardness of organoelement groups

Peregudov

Kravtsov

2001

Appl. Organometal. Chem.

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Q = O, S), containing a great variety of different organometallic groups containing transition or heavy main-group metals. The data on chemical hardness of L n M groups were obtained from NMR study of distribution of different L n M groups between hard and soft anions. The following basic results have been obtained. (1) The relative electronegativity and chemical hardness of L n M groups can change in parallel or not with the electronegativity and hardness of the central metal atom. (2) The substituents in Ar can substantially modify electronegativity and hardness of Ar n M groups; the influence of Ar groups has an inductive nature; the increase in electrondonating ability of aryl ligands enhances the hardness of Ar n M cations. (3) The relative electronegativity and hardness of L n M groups in L n MX are invariant and do not depend on X.

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The influence of aryl ligands on the chemical hardness of triarylitin cations

Cited by 3 publications

References 14 publications

DFT Calculations of ¹¹⁹Sn Chemical Shifts Using Gauge-Including Atomic Orbitals and Their Interpretation via Group Properties

DFT Calculations of ¹¹⁹Sn Chemical Shifts Using Gauge-Including Atomic Orbitals and Their Interpretation via Group Properties

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Electronegativity and chemical hardness of organoelement groups

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The influence of aryl ligands on the chemical hardness of triarylitin cations

Cited by 3 publications

References 14 publications

DFT Calculations of 119Sn Chemical Shifts Using Gauge-Including Atomic Orbitals and Their Interpretation via Group Properties

DFT Calculations of 119Sn Chemical Shifts Using Gauge-Including Atomic Orbitals and Their Interpretation via Group Properties

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Electronegativity and chemical hardness of organoelement groups

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Product

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DFT Calculations of ¹¹⁹Sn Chemical Shifts Using Gauge-Including Atomic Orbitals and Their Interpretation via Group Properties

DFT Calculations of ¹¹⁹Sn Chemical Shifts Using Gauge-Including Atomic Orbitals and Their Interpretation via Group Properties