US EPA

6851252 

Journal Article 

THERMAL CHEMISTRY OF CPMO(NO)(CH2CME3)2 - LEWIS BASE ADDUCTS OF CPMO(NO)(=CHCME3) AND A NEW BONDING MODE FOR NITRIC-OXIDE 

Legzdins, P; Legzdins, P; Rettig, SJ; Rettig, SJ; Veltheer, JE; Veltheer, JE; Batchelor, RJ; Batchelor, RJ; Einstein, FWB; Einstein, FWB 

1993 

1 

Organometallics
ISSN: 0276-7333
EISSN: 1520-6041 

12 

9 

3575-3585 

10.1021/om00033a033 

WOS:A1993LX17200033 

Treatment of CpMo(NO)Cl2 with (Me3CCX2)2Mg-X(dioxane) [X = H, D] in THF at low temperatures provides moderate yields of the bis(neopentyl) complexes, CpMo(NO)(CH2CMe3)2 (1) and CpMo(NO)(CD2CMe3)2 (1-d4). The solid-state molecular structure of 1-d4 has been determined at 170 K. Crystals of 1-d4 are monoclinic of space group P2(1)/n; a = 5.9781(6) angstrom, b = 20.065(4) angstrom, c = 13.6355(17) angstrom; beta = 95.52(1)-degrees; Z = 4; R = 0.025, R(w) = 0.032 for 2494 reflections with I greater-than-or-equal-to 2.5sigma(I). Room-temperature thermolysis of 1 in CH2Cl2 solution provides bimetallic [CpMo(NO)](mu-eta1:eta2-NO)(mu-CHCMe3) [CPMo[=CHCMe3)] (2) in which the unprecedented mu2-eta1:eta2-NO ligand formally provides five electrons to the two Mo centers. Crystals of 2 are orthorhombic of space group Pcab: a = 17.836(2) angstrom, b = 18.265(2) angstrom, c = 13.198(2) angstrom; Z = 8; R = 0.042, R(w) = 0.037 for 4081 reflections with I greater-than-or-equal-to 3sigma(I). Thermolysis of 1 in the presence of phosphines or pyridine (L) provides the monomeric adducts, CpMo(NO)(=CHCMe3)(L) (3-5, 7) of which CpMo(NO)(=CHCMe3)(PPh2Me) (3) has been crystallographically characterized. Crystals of 3 are monoclinic of space group P2(1)/n: a = 9.328(2) angstrom, b = 15.516(3) angstrom, c = 15.188(2) angstrom, beta = 93.72(1)-degrees; Z = 4; R = 0.027, R(w) = 0.026 for 3406 reflections with I greater-than-or-equal-to 3sigma(I). Thermolysis of 1 in the presence of excess PMe3 in CH2Cl2 affords [(Me3P)4Mo(NO)Cl]2 (6). Displacement of pyridine (py) from CpMo(NO)(=CHCMe3)(PY) (7) with a stoichiometric amount of PMe3 produces CpMo(NO)(=CHCMe3)(PMe3)(8). Reaction of 1 with CNCMe3 yields the eta2-iminoacyl complex, CpMo(NO)(eta2-C{NCMe3}CH2CMe3)(CH2CMe3) (9).<