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Solid‐State NMR and EXAFS Spectroscopic Characterization of Polycrystalline Copper( I ) O , O ′‐Dialkyldithiophosphate Cluster Compounds: Formation of Copper( I ) O , O ′‐Diisobutyldithiophosphate Compounds on the Surface of Synthetic Chalcocite
Author(s) -
Rusanova Daniela,
Pike Kevin J.,
Persson Ingmar,
Hanna John V.,
Dupree Ray,
Forsling Willis,
Antzutkin Oleg N.
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200501490
Subject(s) - chalcocite , copper , crystallite , crystallography , chemistry , extended x ray absorption fine structure , magic angle spinning , nuclear magnetic resonance spectroscopy , analytical chemistry (journal) , spectroscopy , nmr spectra database , solid state nuclear magnetic resonance , absorption spectroscopy , stereochemistry , nuclear magnetic resonance , spectral line , chalcopyrite , organic chemistry , physics , quantum mechanics , astronomy
A number of polycrystalline copper( I ) O , O ′‐dialkyldithiophosphate cluster compounds with Cu 4 , Cu 6 , and Cu 8 cores were synthesized and characterized by using extended X‐ray absorption fine‐structure (EXAFS) spectroscopy. The structural relationship of these compounds is discussed. The polycrystalline copper( I ) O , O ′‐diisobutyldithiophosphate cluster compounds, [Cu 8 {S 2 P(O i Bu) 2 } 6 (S)] and [Cu 6 {S 2 P(O i Bu) 2 } 6 ], were also characterized by using 31 P CP/MAS NMR (CP = cross polarization, MAS = magic‐angle spinning) and static 65 Cu NMR spectroscopies (at different magnetic fields) and powder X‐ray diffraction (XRD) analysis. Comparative analyses of the 31 P chemical‐shift tensor, and the 65 Cu chemical shift and quadrupolar‐splitting parameters, estimated from the experimental NMR spectra of the polycrystalline copper( I ) cluster compounds, are presented. The adsorption mechanism of the potassium O , O ′ ‐ diisobutyldithiophosphate collector, K[S 2 P(O i Bu) 2 ], at the surface of synthetic chalcocite (Cu 2 S) was studied by means of solid‐state 31 P CP/MAS NMR spectroscopy and scanning electron microscopy (SEM). 31 P NMR resonance lines from collector‐treated chalcocite surfaces were assigned to a mixture of [Cu 8 {S 2 P(O i Bu) 2 } 6 (S)] and [Cu 6 {S 2 P(O i Bu) 2 } 6 ] compounds.