ISSN:
0009-2940
Keywords:
Bis(phosphonio)isophosphindolide cations
;
Silver complexes
;
31P NMR
;
109Ag NMR
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The outcome of reactions of bis(phosphonio)isophosphindolide salts 1[X] and 6[X] (X- = Cl-, Br-, CF3SO3-) with silver salts AgY (Y- = CF3SO3-, CF3CO2-, CH3CO2-, 1/2 SO4-) depends strongly on the available anions X, Y. If X-, Y- = CF3SO3-, both mononuclear and dinuclear silver complexes are formed which exhibit either μ1,μ1(P) or μ2,η1(P) coordination of the cations 1, 6 to one or to both metals. In solution, dynamic equilibria between both types of products and free 1, 6 were detected by 31P-NMR spectroscopy. Mononuclear (4a, 7) and dinuclear (5a, 8) complexes were isolated as solvates with CHCl3 or THF. If X-, Y- = CF3CO2, only equilibrium mixtures between the free ligands and silver complexes and no isolable products were obtained. 31P-NMR investigations revealed a preference for the formation of dinuclear complexes. Anion metathesis and precipitation of AgX were observed for X- = Cl-, Br-. No coordination of 1, 6 to Ag+ took place in the case of Y- = CH3CO2-, SO42-. The formed complexes were characterised in solution by 31P- and in part by 109Ag-NMR spectroscopy. Complexes 7, 8 were further studied by single crystal X-ray diffraction which revealed the presence of a THF molecule coordinated to silver in both cases. The μ2-coordinated cation 1 is the only bridging ligand in 8, whereas the presence of additional μ2-CF3CO2 ligands was deduced from the results of 31P,31P EXSY measurements in the case of the trifluoroacetato complexes.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961290315
Permalink
