Crystal Structure and Coordination Chemistry of the Pentane-Soluble Sodium Salt of an Oxygen Tripod Ligand

Article abstract of DOI:10.1021/ja00235a025

The sodium salt of the anionic halfsandwich complex 3>^- <*> L^-crystallizes as trimeric aggregate (NaL)3*2H2O.Crystal data are as follows: a = 10.866 (2) Angstroem, b = 25.048 (4) Angstroem, c = 31.378 (9) Angstroem, β = 98.77 (2)deg, Z = 4, d_calcd = 1.35 gcm^-3, and space group P2₁/c.The complex anion L^- reacts as an oxygen tripod ligand with M(CO)6 to form ^- (1a, M = Mo, 1b, M = W). 1areacts with allyl iodide to give 3-C3H5)>.The hydride complexes (2a,b), obtained by protonation of 1a,b, undergo insertion reactions with isoprene to give the allyl complexes 3-C5H9)>. 2b can be halogenated to give , X = Cl, Br, and I. 2b is oxidized by air to yield the tungsten oxo complex L2W2O6.The ML2 complexes , PF6, PF6, and (PF6)2 have been prepared from the reaction of NaL in water or tetrahydrofuran with oxovanadium (IV), vanadium(III), chromium(III), and titanium(III) salts.The mixed ligand complexes , , , PPh4, and <2> have been synthesized likewise.