Phosphinines and donor-substituted phosphinines are of recent interest due to their use in homogeneous catalysis. In this article, a Pd(II) bis(phosphinine) complex was characterised and phosphorus–selenium coupling constants were used to assess the donor properties of the diphenylphosphine substituents of phosphinine ligands to promote their further use in catalysis. The selenation of 2,5-bis(diphenylphosphino)-3,6-dimethylphosphinine (5) and 2-diphenylphosphino-3-methyl-6-trimethylsilylphosphinine (6) gave the corresponding phosphine selenides 8 and 9, respectively, leaving the phosphinine ring intact. Multinuclear NMR spectroscopy, mass spectrometry and single crystal X-ray diffraction confirmed the oxidation of all the diphenylphosphine substituents with 1JP-Se coupling constants determined to be similar to SePPh3, indicating that the phosphinine rings were electronically similar to phenyl substituents. Solutions of 6 were found to react with oxygen slowly to produce the phosphine oxide 10 along with other by-products. The reaction of [bis{3-methyl-6-(trimethylsilyl)phosphinine-2-yl}dimethylsilane] (4) with [PdCl2(COD)] gave the chelating dichloropalladium(II) complex, as determined by multinuclear NMR spectroscopy, mass spectrometry and an elemental analysis. The molecular structure of the intermediate 2 in the formation of 4,6-di(tert-butyl)-1,3,2-diazaphosphinine (3) was also determined, which confirmed the structure of the diazaphosphacycle P(Cl){N=C(tBu)CH=C(tBu)-N(H)}.

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.