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Co-ordination Chemistry of Sulphines. Part 5. ?-S ang η-SCS Co-ordination of Sulphines to Rhodium(1). Fluxional Behaviour of ICl-(PR3)(XYCSO)> (R=alkyl; X,Y=aryl, S-aryl, S-alkyl, or Cl) Complexes and Influence of Suphine Geometry on the Formation of ICl(PR3)2(XYCSO)>.

DOI: 10.1039/DT9820000397

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 397 - 406 (1982)

Update date:2022-08-05

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Authors:

Gosselink, Johan W.Gosselink, Johan W.

Brouwers, Anja M. F.Brouwers, Anja M. F.

Koten, Gerard vanKoten, Gerard van

Vrieze, KeesVrieze, Kees

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Article abstract of DOI:10.1039/DT9820000397

Sulphines react with <ICl(cyclo-C8H14)2>2> and PR3 (R=C6H11 or iPr) to afford complexes of the type ICl(PR3)n(sulphine)> (n=1 or 2), in which the number of phosphines depends on the nature of the sulphine side bonds.If no reactive (C-S, C-Cl) side bonds are present, the sulphine co-ordinates via ?-S to RhI with two phosphines in trans positions.If one of two C-S side bonds are present the sulphine co-ordinates η3-SCS to a phosphines in trans positions.None of these complexes undergoes a C-S oxidative-addition reaction.For the η3-SCS to co-ordinated complexes ICl(PR3)<(E)-(MeS)(p-MeC6H4)CSO>> and ICl(PR3)<(E)(R'S)2CSO>> (R=C6H11 or iPr, R'=C6H4-Me-p or Ph) a fluxional process is found (31P and 1H n.m.r.), which can be described either as an (E)-(Z) isomerization of the MeS, p-MeC6H4S, or PhS group of the co-ordinated side bonds or as an intramolecular PR3-Cl interchange.For the corresponding (Z) stereoisomers this process could not be detected.The complex ICl<(E)-(MeS)(p-MeC6H4)CSO>>,(E)-(2b), and P(C6H11)3 form an equilibrium mixture with trans-ICl2<(E)-(MeS)(p-MeC6H4)CSO>>, (E)-(4b), in which the sulphine is ?-S co-ordinated.On the other hand the corresponding (Z) stereoisomer, (Z)-(2b), is in equilibrium with P(C6H11)3 and cis-ICl2<(Z)-(MeS)(p-MeC6H4)CSO>>, (Z)-(6b), a five-co-ordinate rhodium(I) complex with an η3-SCS co-ordinated sulphine.This difference between the (E) and (Z) stereoisomers can be understood in terms of the geometric arrangement of the pseudo-allylic co-ordination.

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