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

Topics:

Authors:

Gosselink, Johan W.

Brouwers, Anja M. F.

Koten, Gerard van

Vrieze, Kees

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

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 Rh^I 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.

Full text of DOI:10.1039/DT9820000397

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:(CH₃C₆H₄S)2CSO

Cas No:77280-37-6

R&D Labs maybe for 77280-37-6

shanghai jinshan pharmaceutical Co.,Ltd

Contact:021-57363011，13681638167

Address:No. 7966 Tingfeng Road,Jinshan,Shanghai,China
Liaoyang Xinyou Chemical Products Co.,Ltd.

Contact:+86-419-5165433 13604191870

Address:Huishang Road6-1, Hongwei District, Liaoyang, Liaoning, China
NanJing Rate Biochemicals CO., LTD

Contact:+86-25-84931986

Address:NO. 1 Hongjing Road,Jiangning Science Park,Nanjing,China
SHIJIAZHUANG HENRYTE CHEMICALS CO,.LTD(expird)

Contact:+86-311-85208698 311-80837698

Address:NO.166, yuhua west road, SHIJIAZHUANG, China
Qingdao XinYongAn Chemicals Co., Ltd

Contact:+86-532-81107967

Address:Chengyang dual-port industrial park by the sea，Qingdao

Relevant to this article

Reactions of N,N-Dimethylvinylamine with Electron-Poor Olefins

Doi:10.1021/jo00140a021
(1982)
2-TRIMETHYLSILYLOXY-4-METHOXYFURAN: AN EXCELLENT SYNTHON FOR THE PRODUCTION OF 5-SUBSTITUTED TETRONATES (4-METHOXYBUTENOLIDES).

Doi:10.1016/S0040-4039(00)86829-X
(1982)
THERMAL REACTIONS OF PHENYL DERIVATIVES OF DIMETHYLSULFONIUM 1-AROYL-6-OXO-2,4-HEXADIENYLIDE. A REMARKABLE EXAMPLE OF REACTIONS CONTROLLED BY INTRAMOLECULAR STERIC INTERFERENCES

Doi:10.1246/cl.1982.763
(1982)
The bromination-methanolysis of N-acetyl-2,3-dimethylindole

Doi:10.1139/v82-181
(1982)
Doi:10.1039/jr9490000703
(1949)
Synthesis of 1,2-dihydro-3H-pyrrolo[1,2-a]pyrrole-1-carboxylic acids and homologous pyridine and azepine analogues thereof

Doi:10.1139/v82-328
(1982)

Article Doi