RESUMO
Treating [Li(tmeda)]2[Zr(CH3)6] with aryl thiols, HSC6H4-4-R, in a 1:6 stoichiometry in diethyl ether affords excellent yields of [Li(tmeda)]2[Zr(SC6H4-4-R)6], where R = CH3 (1(2-)) or OCH3 (2(2-)) and tmeda denotes N,N,N',N'-tetramethylethylenediamine. These complexes are air-sensitive canary-yellow solids, soluble in hexane, diethyl ether, THF, and acetonitrile, that form yellow single crystals of [Li(tmeda)](2)1 (diethyl ether solution) or [Li(THF)3](2)2 (THF solution) from saturated solutions at -20 degrees C. Both complexes were characterized by X-ray crystallography and consist of a zirconium atom coordinated solely by the sulfur atoms of six aryl thiolate ligands in a nonoctahedral geometry. In each structure the lithium cation coordinates to the three sulfur atoms on the triangular faces of the S6 pseudotrigonal prism. These lithium-sulfur interactions appear to play a role in determining the coordination geometry about the metal center by orienting the sulfur lone pairs of electrons slightly out of the plane defined by the S3 triangular face and tilted away from the zirconium atoms. A likely consequence is the positioning of the sulfur lone pairs of electrons away from orthogonality with the zirconium-sulfur vector, and hence, they are poorly arranged to pi-interact with zirconium. Complex 1(2-) with a twist angle of ca. 9.18 degrees (trigonal prism, 0 degree; octahedron, 60 degrees) agrees with the interpretations of computational studies on d degree complexes, which suggest that a nearly trigonal prismatic geometry is favored when the interaction between metal and ligand is primarily through sigma-bonds. The intrinsically weak pi-donor thiolate ligand is probably converted to a primarily sigma-bonding system by the lithium-sulfur interaction. On the other hand complex 2(2-) with a twist angle of ca. 30.38 degrees is trigonally twisted to the midpoint of the trigonal prismatic-to-octahedral reaction coordinate. In complex 2(2-) the 4-OCH3 group is an electron donor by resonance effects that possibly may lead to the movement away from the expected trigonal prismatic geometry due to either pi-interactions or electrostatics repulsion.
RESUMO
We have previously shown that intrathecal (i.t.) morphine, but not the alpha 2-adrenoreceptor agonist clonidine, administered prior to sciatic nerve section, reduced the level of autotomy in rats, which is a behavioural model of neuropathic pain. Neither drug was effective when administered 15 min after nerve section. We now examined the effects of i.t. morphine and clonidine on the development of flexor reflex hyperexcitability following sciatic nerve section in acute physiological experiments. The flexor reflex was recorded from the hamstring muscles in decerebrate, spinalized, unanesthetized rats. The effect of sciatic nerve section on the flexor reflex without drugs was compared with axotomy performed 60 min after i.t. injection of 3 micrograms or 30 micrograms morphine, as well as 50 micrograms clonidine. The effect of these drugs on reversing reflex hyperexcitability was also examined. Both doses of morphine administered prior to sciatic nerve section profoundly depressed the baseline reflex and the higher dose almost completely abolished reflex hyperexcitability following nerve section. In contrast, clonidine pre-administration was less effective in depressing the baseline reflex and blocked reflex hyperexcitability less than morphine. Both morphine and clonidine administered 15 min after nerve section reversed spinal hyperexcitability. Thus, the ability of morphine to prevent the occurrence of autotomy may be related to its effectiveness in blocking axotomy-induced hyperexcitability. These physiological data suggest that even a short period of spinal cord hyperexcitability following nerve injury may lead to the development of neuropathic pain.
