University of Surrey

Test tubes in the lab Research in the ATI Dance Research

Some Complexes Containing Donor Sulphur Atoms.

Murphy, John Michael. (1966) Some Complexes Containing Donor Sulphur Atoms. Doctoral thesis, University of Surrey (United Kingdom)..

Available under License Creative Commons Attribution Non-commercial Share Alike.

Download (6MB) | Preview


Complexes of o-aminobenzenethiol have been obtained with divalent chromium, manganese, iron, cobalt, nickel and zinc. In addition, o-aminobenzenethiolcopper(I), bis(o-iminobenzenethiol)-nickel, tris(o---aminobenzenethiol)cobalt(III) and oxobis(o-amino-benzenethiol)vanadium(lV) have been prepared. Copper(ll) and iron(III) complexes could not be obtained because the ligand reduces copper(II) and iron(III) salts. The blue compound formed by oxidation of bis(o-aminoben-zenethiol)nickel(II) in sodium hydroxide has been shown to be bis(o-iminobenzenethiol)nickel and not an oxygen-bridged nickel(IV) compound as suggested by earlier workers. The dark blue substance which had been claimed to be bis(o-aminobenzenethiol)cobalt(Il) has now been shown to be a mixture of tris(o---aminobenzenethiol)---cobalt(III) and a cobalt oxide, peroxide or hydroxide species. However, it has not been possible to establish the exact nature of this species. The true cobalt(Il) complex is orange-brown and high-spin, not low-spin as was previously thought. Bis(o-amino-benzenethiol)iron(II) is antiferromagnetic with a Neel point at 138°K and an exchange coupling constant of 22.2cm[-1]. It is probable that sulphur bridging is present in many of the o-aminobenzenethiol complexes with divalent metals thereby producing six-coordinate polymeric structures. o-Aminobenzenethiol produces a slightly stronger ligand field than water. Although pure chromium(II) - thiourea complexes could not be obtained, compounds analysing approximately as dichlorobis(thiourea)chromium(II) and hexakis(thiourea)-chromium(II) perchlorate were prepared. In both compounds the thiourea is coordinated through sulphur, and in the chloride antiferromagnetic behaviour suggests either a chlorine- or sulphur-bridged structure. Bis(diethyldithiocar-bamate)chromium(II) has been prepared, but attempts to prepare bis(2-aminoethanethiol)chromium(II) and bis(ethyl xanthate)chromium(II) were unsuccessful.

Item Type: Thesis (Doctoral)
Divisions : Theses
Authors :
Murphy, John Michael.
Date : 1966
Contributors :
Additional Information : Thesis (Ph.D.)--University of Surrey (United Kingdom), 1966.
Depositing User : EPrints Services
Date Deposited : 22 Jun 2018 15:15
Last Modified : 06 Nov 2018 16:54

Actions (login required)

View Item View Item


Downloads per month over past year

Information about this web site

© The University of Surrey, Guildford, Surrey, GU2 7XH, United Kingdom.
+44 (0)1483 300800