TY - JOUR
T1 - Digold Phosphinine Complexes Are Stable with a Bis(Phosphinine) Ligand but Not with a 2-Phosphinophosphinine
AU - Cleaves, Peter A.
AU - Gourlay, Ben
AU - Marseglia, Margot
AU - Ward, Daniel J.
AU - Mansell, Stephen M.
PY - 2022/11/11
Y1 - 2022/11/11
N2 - The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (19) with one and two equivalents of [AuCl(tht)] was attempted in order to selectively form the mono and digold species, respectively. The digold species [(AuCl)2(19)] (21) was synthesized in 32% yield and comprehensibly characterized (multinuclear NMR spectroscopy, elemental analysis, mass spectrometry and single-crystal X-ray diffraction). The monogold species showed no 31P nuclear magnetic resonance at 25 °C but two resonances at −70 °C due to rapid exchange of AuCl between the phosphinine donors at 25 °C and was also susceptible to redistribution reactions to form the digold species. Analogous reactions of [AuCl(tht)] with 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (22) revealed preferential coordination of the AuCl unit to the PPh2 donor first, with coordination to the phosphinine achieved upon reaction with the second equivalent of [AuCl(tht)]. Unexpectedly, the digold complex was not stable, undergoing decomposition to give an unidentified black precipitate. Structural information could only be obtained on the digold hydrolysis product [(AuCl)2(1-OH-2-PPh2-3-MePC5H4)], which showed an aurophilic interaction.
AB - The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (19) with one and two equivalents of [AuCl(tht)] was attempted in order to selectively form the mono and digold species, respectively. The digold species [(AuCl)2(19)] (21) was synthesized in 32% yield and comprehensibly characterized (multinuclear NMR spectroscopy, elemental analysis, mass spectrometry and single-crystal X-ray diffraction). The monogold species showed no 31P nuclear magnetic resonance at 25 °C but two resonances at −70 °C due to rapid exchange of AuCl between the phosphinine donors at 25 °C and was also susceptible to redistribution reactions to form the digold species. Analogous reactions of [AuCl(tht)] with 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (22) revealed preferential coordination of the AuCl unit to the PPh2 donor first, with coordination to the phosphinine achieved upon reaction with the second equivalent of [AuCl(tht)]. Unexpectedly, the digold complex was not stable, undergoing decomposition to give an unidentified black precipitate. Structural information could only be obtained on the digold hydrolysis product [(AuCl)2(1-OH-2-PPh2-3-MePC5H4)], which showed an aurophilic interaction.
U2 - 10.3390/inorganics10110203
DO - 10.3390/inorganics10110203
M3 - Article
SN - 2304-6740
VL - 10
JO - Inorganics
JF - Inorganics
IS - 11
M1 - 203
ER -