The compounds Y[N(QPPh2)2]3 (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reactions between Y[N(SiMe3)2]3 and HN(QPPh2)2 in methylene chloride (CH2Cl2). The compounds are not isostructural. In 1, the Y atom is surrounded by three similar [N(SPPh2)2]- ligands bound η3 through two S atoms and an N atom. The molecule possesses D3 symmetry, as determined in the solid state by X-ray crystallography and in solution by 89y and 31P NMR spectroscopies. In 2, the Y atom is surrounded again by three [N(SePPh2)2]- ligands, but two are bound η2 through the two Se atoms and the other ligand is bound η3 through the two Se atoms and an N atom. Although a fluxional process is detected in the 31P and 77Se NMR spectra, a triplet is found in the 89Y NMR spectrum of 2 (δ = 436 ppm relative to YCl3 in D2O, 2J(Y-P) = 5 Hz). This implies that on average the conformation, of one η3- and two η2-bound ligands is retained in solution. Crystallographic data for 1: C72H60N3P6S6Y, rhombohedral, R3c, a = 14.927(5) Å, c = 56.047(13) Å, V = 10815(6) Å3, T = 153 K, Z = 6, and R1(F) = 0.042 for the 1451 reflections with I > 2σ(I). Crystallographic data for 2: C72H60N3P6Se6Y·CH2Cl2, monoclinic, P21/n, a = 13.3511(17) Å, b = 38.539(7) Å, c = 14.108(2) Å, β = 94.085(13)°, V = 7241(2) Å3, T = 153 K, Z = 4, and R1(F) = 0.037 for the 8868 reflections with I > 2σ(I).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry