Bis(cyclopentadienyl)yttrium Complexes of the Ligand [N(QPPh₂)₂]^- (Q = S, Se):  Synthesis, Structure, and NMR Properties of Cp₂Y[η³-N(QPPh₂)₂]

Abstract

The compounds Cp(2)Y[eta(3)-N(QPPh(2))(2)] (Q = S (1), Se (2)) have been synthesized in good yield from the protonolysis reaction between Cp(3)Y and HN(QPPh(2))(2) in tetrahydrofuran. In both compounds, the [N(QPPh(2))(2)](-) ligand is bound eta(3) to the Y center which, in 1, represents the first example of that mode of binding for the sulfur-containing ligand. The Y atom is also coordinated to two (C(5)H(5))(-) ligands and so is formally 9-coordinate. Both 1 and 2 are stable in inert environments for prolonged periods of time. Each is soluble in THF and CH(2)Cl(2). (1)H, (31)P, (77)Se, and (89)Y NMR data were collected to lend insight into the solution properties of these molecules. Crystallographic data for 1 (-120 degrees C): C(34)H(30)NP(2)S(2)Y, triclinic, P&onemacr;, a = 9.685(5) Å, b = 12.176(6) Å, c = 13.978(7) Å, alpha = 87.382(9) degrees, beta = 87.358(9) degrees, gamma = 68.689(9) degrees, V = 1533(1) Å(3), Z = 2, and R(1)(F) = 0.047 for the 4023 reflections with I > 2sigma(I). Crystallographic data for 2 (-120 degrees C): C(34)H(30)NP(2)Se(2)Y, triclinic, P&onemacr;, a = 9.745(5) Å, b = 12.222(6) Å, c = 13.930(7) Å, alpha = 88.024(9) degrees, beta = 87.380(9) degrees, gamma = 69.137(9) degrees, V = 1548(1) Å(3), Z = 2, and R(1)(F) = 0.056 for the 4324 reflections with I > 2sigma(I).