Soft metal ion-promoted reactions of organo-sulphur compounds

Author(s):  
D. P. N. Satchell ◽  
R. S. Satchell
2014 ◽  
Vol 12 (11) ◽  
pp. 1101-1126 ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Clive Holloway

AbstractThis review classifies and analyzes heterohexanuclear platinum clusters into seven types of metal combinations:Pt5M, Pt4M2, Pt3M3, Pt2M4, PtM5, Pt2M3M′, and Pt2M2M2′. The crystals of these clusters generally belong to six crystal classes: monoclinic, triclinic, orthorhombic, tetragonal, trigonal and cubic. Among the wide range of stereochemistry adopted by these clusters, octahedral and capped square-pyramidal are the most common. Although platinum is classified as a soft metal atom, it bonds to a variety of soft, borderline and hard metals. Nineteen different heterometal ions are involved in hexanuclear platinum clusters. The shortest Pt-M bond distance in the case of M being a non-transition element is 2.395(4) Å for germanium and for M being a transition metal ion it is 2.402(2) Å for Cobalt. The shortest Pt-Pt bond distance observed in these clusters is 2.532 Å. Several relationships between the structural parameters are identified and discussed. Some clusters exist in two isomeric forms and some show crystallographically independent molecules within the same crystal. Such isomers and independent molecules are examples of distortion isomerism.


1999 ◽  
Vol 46 (3) ◽  
pp. 567-580 ◽  
Author(s):  
A Krezel ◽  
W Bal

The metal ion coordination abilities of reduced and oxidized glutathione are reviewed. Reduced glutathione (GSH) is a very versatile ligand, forming stable complexes with both hard and soft metal ions. Several general binding modes of GSH are described. Soft metal ions coordinate exclusively or primarily through thiol sulfur. Hard ones prefer the amino acid-like moiety of the glutamic acid residue. Several transition metal ions can additionally coordinate to the peptide nitrogen of the gamma-Glu-Cys bond. Oxidized glutathione lacks the thiol function. Nevertheless, it proves to be a surprisingly efficient ligand for a range of metal ions, coordinating them primarily through the donors of the glutamic acid residue.


1984 ◽  
Vol 62 (1) ◽  
pp. 49-54 ◽  
Author(s):  
D. J. Farmer ◽  
B. R. Hollebone

The in vitro inhibition of hydroxymethylbilane synthase (EC 4.3.1.8, uroporphyrinogen I synthetase) obtained from livers of Sprague–Dawley rats has been studied with a wide range of di- and tri-valent metal ions. After purification by cell lysis, heat treatment, and centrifugation, the stable, soluble enzyme yielded sigmoidal inhibition curves with increasing concentrations of each of the 16 test ions. Using the negative logarithm of metal concentration for 50% inhibition (the pM50 value), the metal ions could be classified according to their Klopman hardness values. Very soft ions including Hg2+, intermediate ions including Cr3+, and very hard ions including Al3+ all yielded large pM50 values indicating strong inhibition. In comparison to known metal-ion chemical behaviour, these three ions could indicate three different types of inhibitory binding sites at or near the active site: Hg2+ corresponding to sulfur in cysteine, Cr3+ corresponding to nitrogen in histidine, and Al3+ corresponding to oxygen in carboxyl groups. The presence of the first two sites is also indicated by the pH dependence of activity.


ChemInform ◽  
2010 ◽  
Vol 25 (25) ◽  
pp. no-no
Author(s):  
D. P. N. SATCHELL ◽  
R. S. SATCHELL

1999 ◽  
Vol 181 (19) ◽  
pp. 5891-5897 ◽  
Author(s):  
Christopher Rensing ◽  
Mallika Ghosh ◽  
Barry P. Rosen
Keyword(s):  

2006 ◽  
Vol 05 (01) ◽  
pp. 87-98 ◽  
Author(s):  
AFSHAN MOHAJERI ◽  
MARYAM ABASI

Ab initio calculations were performed to study the applicability and reliability of the semi quantitative model based on the local hard-soft acid-base principle in studying the interaction of metal ions with ligands. The particular attention is devoted to the interaction of CO , CN - and SCN - as the base with some hard metal ions ( Li +, Na +, K +) and some soft metal ions ( Pd +2, Ag +2, Cd +2) as acids. The interaction energies were calculated using the HSAB principle and compared with the values obtained by the conventional MP2 method. The results show that the HSAB principle does not work in many cases and it fails to predict correct values for interaction energies. The AIM and NBO analyses were also performed to characterize the nature of the metal ion-ligand interaction. It is found that the charge transfers have great significance in the interaction of metal ions with ligands.


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