The synthesis of polydentate phosphines: Characterization of bis-phosphines and polydentate phosphines by electrospray mass spectrometry and nuclear magnetic resonance spectroscopy.

摘要

The coordination chemistry of Ag (I) with bis-phosphines of the type Ph2P(CH2)nPPh2 (n = 3, 4, or 12) was studied in solution by variable temperature 31P {lcub} 1H{rcub} NMR. Utilizing the observed coupling constants, coordination numbers of one, two, and four were seen for Ag (I). These studies were complemented by electrospray mass spectrometry.; In addition, solid-state structures of [Ag2(dppp)2](BF 4)2 and [Ag2(dppb)2](BF4) 2 were determined and found to be in agreement with solution structures from the 31P {lcub}1H{rcub} NMR and electrospray mass spectrometry studies.; The long chain tetraphosphines Ph2P(CH2)3 P(Ph)(CH2)3(Ph)P(CH2)3PPh 2 (n = 4 or 12) were synthesized. The synthetic pathway for these tetraphosphines involved production of the corresponding phosphonium salts and phosphine oxides. All products were characterized by 31P {lcub}1H{rcub} NMR and mass spectrometric techniques (ESMS or FAB). Complexation involving Ag (I) with the ligands was studied by variable temperature 31P {lcub}1H{rcub} NMR and ESMS.; The long chain triphosphine Ph2P(CH2)3P(Ph)(CH 2)12PPh2 was synthesized. In addition to the ligand, the corresponding phosphonium salt and phosphine oxide were characterized by 31P {lcub}1H{rcub} NMR and mass spectrometric techniques (ESMS or FAB).