185340-49-2Relevant academic research and scientific papers
Structural and spectroscopic studies on copper, silver and gold complexes of mixed phosphathia ligands and their chalcogenide derivatives
Genge, Anthony R. J.,Gibson, Alexander M.,Guymer, Naomi K.,Reid, Gillian
, p. 4099 - 4107 (2007/10/03)
Reaction of [Cu(MeCN)4]PF6 or AgBF4 with 1 molar equivalent of Ph2P(E)(CH2)2SZS(CH2) 2(E)PPh2 [Z = (CH2)2, E = S (L1b) or Se (L1c); Z = (CH2)3, E = none (L2a), S (L2b) or Se (L2c); Z = o-C6H4, E = none (L3a), S (L3b) or Se (L3c)] in degassed acetone followed by addition of diethyl ether yielded the mononuclear complexes [ML]X (M = Cu, X- = PF6-; M = Ag, X- = BF4-) in high yield. The gold(I) species [AuL]PF6 were obtained by reaction of L (= L1b, L1c, L2b, L2c or L3a-L3c) with 1 molar equivalent of [AuCl(tht)] (tht = tetrahydrothiophene) and TlPF6. All of these products have been characterised by 1H, 31P-{1H} (and in some cases 77Se-{1H} and 109Ag) NMR and IR spectroscopy, FAB or electrospray mass spectrometry and microanalyses. The data indicate four-co-ordination for all of the copper(I) and silver(I) species and this assignment has been confirmed by single-crystal structure determinations on three copper(I) examples. Spectroscopic studies on [AuL]PF6 indicated linear two-co-ordination on average, via the phosphine, phosphine sulfide or phosphine selenide functions as appropriate. Variable-temperature 31P-{1H} (and 77Se-{1H}) studies showed that the chalcogenide complexes are considerably more labile in solution than the phosphathia ligand complexes. Crystal structure determinations on [CuL3a]+, [CuL1c]+, [AgL1c]+ and [CuL2b]+ each showed the metal ion co-ordinated to all four donor atoms of a single ligand in the solid state, giving an overall distorted-tetrahedral stereochemistry. In the case of [CuL1c]+ there is a slight lengthening of the P-Se bond length compared to that of the unco-ordinated form of L3c. Syntheses for the new pro-ligands are also detailed.
