77280-37-6Relevant academic research and scientific papers
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)>.
Gosselink, Johan W.,Brouwers, Anja M. F.,Koten, Gerard van,Vrieze, Kees
, p. 397 - 406 (1982)
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)> and ICl(PR3)> (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)-(2b), and P(C6H11)3 form an equilibrium mixture with trans-ICl2>, (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)-(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.
