Nucleophilic Discrimination and the trans Effect. The Kinetics of Displacement of X from trans-n- (L=Me2SO, Et2S, PMe3, PEt3, PPh3, or AsEt3; X=Cl, n=1; X=MeOH, n=0) by Neutral and Anionic Nucleophiles

DOI: 10.1039/DT9880002347

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2347 - 2352 (1988)

Update date:2022-07-29

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Authors:

Tobe, Martin L.

Treadgold, Andrew T.

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Article abstract of DOI:10.1039/DT9880002347

The kinetics of the reaction trans-^n- + L' <*> trans-^n'- + X (X=Cl^-, n=1, L=Me2SO, Et2S, PMe3, PEt3, PPh3, or AsEt3, L'=pyridine (py), Me2S, Et2S, PPh3, Me2SO, thiourea (tu), or NNN'N'-tetramethylthiourea (tmtu), n'=0; L'=Cl^-, Br^-, I^-, or SCN^-, n'=1; X=MeOH, n=0, L'=Cl^-, Br^-, I^-, or SCN^-, n'=1) have been studied in 95percent methanol and 5percent water at 25 deg C.The second-order rate constants, k₂, for the anionic substrates do not follow the usual dependence upon n⁰_Pt, the anionic nucleophiles being much less reactive than predicted.A new nucleophilicity scale, based on ^- as standard substrate, does give linear relationships for all the anionic substrates.The relationship between the nucleophilic discrimination and the nature of the trans ligand is discussed.

Full text of DOI:10.1039/DT9880002347

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