Synthesis of Sulphimide Complexes of Palladium and Platinum. Crystal and Molecular Structure of cis-Dichloro(triphenylphosphine)palladium(II)

DOI: 10.1039/DT9890000497

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Journal of the Chemical Society, Dalton Transactions p. 497 - 504 (1989)

Update date:2022-09-26

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Authors:

Davidson, Jack L.

Preston, Peter N.

Spankie, Sally A. R.

Douglas, Graeme

Muir, Kenneth W.

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Article abstract of DOI:10.1039/DT9890000497

Reactions of (M=Pd or Pt) and K2 with S,S-dimethyl-N-heteroaromatic sulphimides Me2SNR (R=2-pyridyl, 4-methyl-2-pyridyl, 2-pyrimidinyl, 4-methyl-2-pyrimidinyl, or 2-pyrazinyl) give 1:1 adducts trans- (1) in which the sulphimide appears to co-ordinate through the ylide nitrogen according to 1H n.m.r. studies.Reaction of with Me2SNPh gives a bis(sulphimide) complex trans- (2) when M=Pd but when M=Pt a phenylnitrene derivative cis- (3) is obtained.Reactions of complexes (1) with phosphines L=PEt3, PMe2Ph, PMePh2, or PPh3 give 1:1 adducts .CH2Cl2 (4f) revealed that the pyrimidine rather than the sulphimide N atom is the point of attachment of the sulphimide ligand to Pd.Conformational energy calculations suggest that electronic rather than steric factors determine which N atom acts as donor to Pd.The crystals are monoclinic, space group P2₁/n, with a=17.307(6), b=9.182(1), c=17.960(2) Angstroem, β=97.15 grad, R=0.024 for 1999 independent reflections with I>3?(I).N.m.r. studies suggest a trans structure for complex (4e) with sulphimide co-ordination via the pyridyl nitrogen.The isomerism and fluxional behaviour of (4c) and (4d) was studied by variable-temperature n.m.r. spectroscopy.

Full text of DOI:10.1039/DT9890000497

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