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Reactions of diaminophosphenium and 1,3,2‐diazaphospholenium triflates with silver salts
Author(s) -
Gudat Dietrich,
Holderberg Andreas W.,
Kotila Sirpa,
Nieger Martin
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961290416
Subject(s) - trifluoromethanesulfonate , chemistry , silver salts , nmr spectra database , crystal structure , medicinal chemistry , crystallography , single crystal , proton nmr , stereochemistry , spectral line , inorganic chemistry , catalysis , organic chemistry , physics , astronomy
Reaction of bis(diisopropylamino)phosphenium triflate ( 1 [CF 3 SO 3 ]) with silver salts AgY [Y – = CF 3 CO 2 – ( 2a ), CF 3 ‐SO 3 – ( 2b ), CH 3 CO 2 – ( 2c )] affords neutral complexes [{( i Pr 2 N) 2 (Y)P} Ag(OSO 2 CF 3 )] ( 3a–c ). While 3a, c are stable up to ambient temperature, 3b is only stable at low temperature and in equilibrium with the cation 1 . The constitution of 3a–c was derived from multinuclear ( 1 H, 13 C, 31 P, 109 Ag) NMR spectra. Compound 3a was further studied by X‐ray single‐crystal diff ractommetry which showed the presence of dimeric units with μ 2 ‐bridging triflate ligands and three‐coordinate silver atoms with a planar T‐shaped coordination geometry. Reaction of 4‐chloro‐1,3‐bis(2,6‐dimethylphenyl)‐1,3,2‐diazaphospholenium triflate ( 4 [CF 3 SO 3 ]) with 2a, c affords equilibrium mixtures whose 31 P‐ and 109 Ag‐NMR spectra suggested the presence of silver complexes 5a, c with constitutions similar to those of 3a, c besides unreacted cation 4 . No reaction was observed between 4 [CF 3 SO 3 ] and 2b . A common mechanism accounting for the different outcome of the individual reactions will be discussed.