Mixed Chloride/Amine Complexes of Dimolybdenum(II,II). 4. Rotational Isomers of Mo(2)Cl(4)(R-py)(4) (R-py = 4-Picoline, 3,5-Lutidine, and 4-tert-Butylpyridine).
The quadruply bonded dimolybdenum complexes with alkyl-substituted pyridines of the formula Mo(2)Cl(4)(R-py)(4) (R-py = 4-pic (4-methylpyridine) (1), 3,5-lut (3,5-dimethylpyridine) (2), and 4-Bu(t)-py (4-tert-butylpyridine) (3)) have been prepared. Nine different compounds, in which there are 11 independent molecules, have been obtained in crystalline form, and their crystal structures have been investigated by X-ray diffraction. Three types of geometric isomers which differ by the angle of internal rotation about the Mo-Mo axis have been recognized in these structures. The eclipsed structures 1-3a display pyridine ligands opposite to each other across the metal-metal bond and have a virtual symmetry D(2)(h)(). The noncentrosymmetric D(2)(d)() structures 1-3b have each pyridine ligand opposite to a Cl atom. The molecules 3c-f have a partially staggered D(2) geometry with N-Mo-Mo-N torsion angles ranging from 10.4 degrees to 25.2 degrees. As a result of this work it is now clear that Mo(2)Cl(4)(R-py)(4) compounds do not show a preference for D(2)(h)() conformation rather than D(2)(d)() conformation. In fact, they seem unusually unrestricted in their rotational conformation, and packing forces appear to have a major influence on the conformation adopted. Further clarification of this question will require spectroscopic study of solutions.
Cotton
F. Albert
FA
Laboratory for Molecular Structure and Bonding, Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012.
Dikarev
Evgeny V.
EV
Herrero
Santiago
S
Modec
Barbara
B