Aliphatic neodymium alkoxides with sterically demanding ligands. Preparation and x-ray crystal structures of Nd2(OCH-iso-Pr2)6L2 (L = THF, py) and [Nd2(OCH-iso-Pr2)6(.mu.-DME)].infin.

摘要: Reaction of the neodymium tris(silylamide) Nd[N(SiMe[sub 3])[sub 2]][sub 3] with 3 equiv diisopropylmethanol (HOCH-i-Pr[sub 2]) in hexane presence THF yields dimeric Lewis base adduct Nd[sub 2](OCH-i-Pr[sub 2])[sub 6](THF)[sub 2] (1). The ligands are easily replaced pyridine solvent at room temperature to yield 2]-(OCH-i-Pr[sub 6](py)[sub (2). Nd-O bridges alkoxide unit found be quite robust, and reaction 1 neat 1,2-dimethoxyethane (DME) produces Nd(OCH-i-Pr[sub 6]([mu]-DME) (3), which two oxygen atoms each DME molecule link adjacent 6] units form an infinite-chain structure. In solid-state structures 1-3, Nd atom adopts a distorted trigonal bipyramidal geometry, 2]O[sub 6]L[sub core can viewed as NdO[sub 4]L bipyramids joined along common axial-equatorial edge neutral donor ligand L (THF, py, or 1/2 DME) occupying axial position. terminal ND-O distances OR average 2.153(4), 2.146(4), 2.145(6) [angstrom], while bridging 2.381(4), 2.383(9), 2.375(9) [angstrom] for respectively. Nd-O-C angles alkoxides verymore » obtuse 164.9(4), 174.9(4), 171.8(8)[degrees], 2.552(5) 2.604(6) Nd-N distance coordinated is 2.682(5) [angstrom]. Crystal data -161 [degrees]C: monoclinic space group P2[sub 1]/n.« less