Steric Properties of Sulfoxide Ligands. Synthesis and Crystal Structure of mer-

DOI: 10.1039/DT9950001653

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 1653 - 1662 (1995)

Update date:2022-08-02

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Authors:

Calligaris, Mario

Faleschini, Paolo

Todone, Flavia

Alessio, Enzo

Geremia, Silvano

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Article abstract of DOI:10.1039/DT9950001653

Solid and circular cone angles and ligand profiles have been calculated for some sulfoxides, showing that S-bonded ligands are markedly bulkier than O-bonded ligands.An application of the cone angles to complexes of Ru(II) and Ru(III) showed that the bonding mode of sulfoxides appears to be the result of a balance between electronic and steric effects.The complex mer- (dpso = Ph2SO) has been synthesized and structurally characterized: triclinic, space group P<*>, Z = 2 with a = 10.315(3), b = 13.093(4), c = 15.692(5) Angstroem, α = 102.98(2), β = 106.79(1), γ = 102.17(2) deg.Two of the three sulfoxides are O- and one is S-bonded.One dpso-O is trans to dpso-S, while the other is trans to Cl.The co-ordination bond distances are consistent with the trans-influence order O < Cl < S.Strain-energy and conformational-entropy terms of three isomers of mer- have been evaluated through molecular mechanics calculations.The energy difference of 7.6 kcal mol^-1 between the characterized complex and the linkage isomer with two trans dpso-S ligands indicates that the isomer isolated is probably favoured thermodynamically and suggests that the interligand steric interactions play an important role in the isomer stability.

Full text of DOI:10.1039/DT9950001653

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