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(CuI) 3 P 4 S 4 : Preparation, Structural, and NMR Spectroscopic Characterization of a Copper( I ) Halide Adduct with β ‐P 4 S 4
Author(s) -
Reiser Sara,
Brunklaus Gunther,
Hong Jung Hoon,
Chan Jerry C. C.,
Eckert Hellmut,
Pfitzner Arno
Publication year - 2002
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 - 10.1002/1521-3765(20020916)8:18<4228::aid-chem4228>3.0.co;2-v
Subject(s) - heteronuclear molecule , chemistry , crystallography , copper , magnetic dipole–dipole interaction , nuclear magnetic resonance spectroscopy , homonuclear molecule , molecule , nmr spectra database , adduct , stoichiometry , trimer , dipole , spectral line , stereochemistry , dimer , organic chemistry , physics , astronomy
(CuI) 3 P 4 S 4 is obtained by reaction of stoichiometric amounts of CuI, P, and S in evacuated silica ampoules. The yellow compound consists of monomeric β ‐P 4 S 4 cage molecules that are separated by hexagonal columns of CuI. (CuI) 3 P 4 S 4 crystallizes isotypic to (CuI) 3 P 4 Se 4 in the hexagonal system, space group P 6 3 cm (no. 185) with a =19.082(3), c =6.691(1) Å, V =2109.9(6) Å 3 , and Z =6. Three of the four phosphorus atoms are bonded to copper, whereas no bonds between copper and sulfur are observed. The two crystallographically distinct copper sites are clearly differentiated by 65 Cu magic‐angle spinning (MAS) NMR spectroscopy. Furthermore, an unequivocal assignment of the 31 P MAS‐NMR spectra is possible on the basis of homo‐ and heteronuclear dipole–dipole and scalar interactions. Dipolar coupling to the adjacent quadrupolar spins 63, 65 Cu generates a clear multiplet structure of the peaks attributable to P1 and P2, respectively. Furthermore, the utility of a newly developed two‐dimensional NMR technique is illustrated to reveal direct connectivity between P atoms based on ( 31 P– 31 P) scalar interactions.