Chelating and bridging diphosphinoamine (PPh2)2N(iPr) complexes of copper(I) |
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Authors: | Ritu Ahuja Munirathinam Nethaji Ashoka G Samuelson |
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Institution: | Department of Inorganic and Physical chemistry, Indian Institute of Science, Bangalore 560 012, India;Technische Universität Darmstadt, Department of Chemistry, Eduard-Zintl-Institut, Inorganic Chemistry, D-64287 Darmstadt, Germany |
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Abstract: | The ligand bis(diphenylphosphino)isopropylamine (dppipa) has been shown to be a versatile ligand sporting different coordination modes and geometries dictated by copper(I). Most of the molecular structures were confirmed by X-ray crystallography. It is found in a chelating mode, in a monomeric complex when the ligand to copper ratio is 2:1. A tetrameric complex is formed when low ratios of ligand to metal (1:2) were used. But with increasing ratios of ligand to metal (1:1 and 2:1), a trimer or a dimer was obtained depending on the crystallization conditions. Variable temperature 31P{1H} NMR spectra of these complexes in solution showed that the Cu–P bond was labile and the highly strained 4-membered structure chelate found in the solid state readily converted to a bridged structures. On the other hand, complexes with the ligand in a bridging mode in the solid state did not form chelated structures in solution. The effect of adding tetra-alkylammonium salts to solutions of various complexes of dppipa were probed by 31P{1H} NMR and revealed the effect of counter ions on the stability of complexes in solution. |
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