Stereochemistry of reaction of episulfonium salts with ? -donors

Ibragimov, M. A.; Lyubinskaya, O. V.; Smit, V. A.

doi:10.1007/bf00956179

Cited by 1 publication

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“…In fact a few reports on the deliberate synthesis of episulfonium salts have been published. One of these describes the use of a silver salt to abstract chloride ions to facilitate the formation of the episulfonium salt; 23 another report describes the use of very low temperatures to isolate the episulfonium salt. 24 The spontaneous rearrangement described here takes place under ambient conditions without the use of silver salts.…”

Section: Synthesismentioning

confidence: 99%

Synthesis, characterisation and crystal structures of new nickel complexes in S4 coordination spheres; an unprecedented rearrangement during ligand synthesis

Verhagen

Ellis

Lutz

et al. 2002

J. Chem. Soc., Dalton Trans.

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Two new nickel() complexes were synthesized with an S 4 coordination environment. These complexes were synthesized by in situ deprotection of thiouronium salts in the presence of nickel(). The ligands used are 4-mercapto-3,3-methyl-1-phenyl-2-thiabutane (Hbsms) and α,αЈ-bis(4-mercapto-3,3-methyl-2-thiabutyl)-o-xylene (H 2 xbsms). The former is a didentate ligand containing one thioether and one thiolate group and the latter is a dithioether dithiolate tetradentate ligand. The differences between these ligands upon coordination to nickel have been investigated. During the synthesis of these ligands, an unprecedented spontaneous rearrangement occurs, which is very fast and selective to a single product. The complexes were characterized by analytical, spectroscopic and electrochemical methods. The geometry of the nickel complexes is square planar according to the single-crystal X-ray structures. In [Ni(bsms) 2 ] the two ligands are coordinated with the thiolates in trans positions towards each other; in [Ni(xbsms)] the thiolates are in enforced cis positions. [Ni(bsms) 2 ] crystallizes in the triclinic space group P1 and has one centrosymmetric molecule in the unit cell. [Ni(xbsms)] crystallizes in the monoclinic space group P2 1 /c with two independent molecules in the asymmetric unit, however, the differences between these two molecules are very small. The Ni-S distances are 2.1730(4)-2.1909(6) Å and in the common range for thiolates and chelating thioethers.

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Section: Synthesismentioning

confidence: 99%