A 31P Nuclear Magnetic Resonance Investigation of the Structure, Equilibria, and Kinetics of in Solution

DOI: 10.1039/DT9800000776

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 776 - 785 (1980)

Update date:2022-08-05

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Authors:

Mann, Brian E.

Musco, Alfredo

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Article abstract of DOI:10.1039/DT9800000776

The compounds (L = PMe3, PMe2Ph, PMePh2, PEt3 or PBuⁿ3), n3, P(p-tolyl)3, P(CH2Ph)3, PPrⁱ3, or P(C6H11)3>, and i3, P(C6H11)3, or PBu^t2Ph> have been prepared and shown to exist in solution.In the cases of L = PMePh2, PEt3, PBuⁿ3, n = 3 and L = PPrⁱ3, P(C6H11)3, n = 2 it has proved possible to measure the equilibrium constant, ΔH^<*>, and ΔS^<*> for n+1><*>n> + L.For , , , , n3)4>, i3)3> and 3>, the tertiary phosphine exchange is dissociative, while for 13)2> and 2> associative exchange occurs.In the case of and n3)3> both associative and dissociative exchange occur, the relative rates of which depend on the temperature and concentration of free tertiary phosphine.In the cases of i3)2> and2> a marked solvent effect has been found and attributed to possible toluene co-ordination producing in equlibrium with .No evidence is found for steric crowding affecting ΔH^<*> or ΔH⁺⁺, but ΔS^<*> and ΔS⁺⁺ are affected due to interpenetration of the ligands and resulting loss of motional freedom, while previously it has been assumed that interligand steric crowding destabilizes the molecule via enthalpy term.

Full text of DOI:10.1039/DT9800000776

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