, a = 10.3552(7) Angstrom b = 13.7960(18) Angstrom, c = 15.9795(13) Angstrom, alpha = 68.227(7)degrees, beta = 82.983(5)degrees, gamma = 82.496(7)degrees, R = 0.0377 for 5893 observed data] is a close metal carborane, based on an icosahedron, in which the [9]andS(3) ligand has effective C-3 symmetry. In solution at room temperature the macrocyclic ligand of 1 undergoes rapid rotation about an axis through the metal carborane polyhedron, and it is likely that the cage phenyl group is also spinning, the two fluxional processes operating in concert via a geared-type mechanism. Compound 2 [space group Pbca, a = 16.771(3) Angstrom, b = 16.907(3) Angstrom, c = 17.757(4) Angstrom, R = 0.0397 for 2946 observed data] is a pseudocloso metal carborane and has a polyhedral architecture characterized by C(1)... C(2) 2.504(7) Angstrom and Ru(3)... B(6) 2.960(6) Angstrom, as a consequence of intramolecular crowding between the phenyl cage substituents. Phenyl/thiamacrocycle intramolecular crowding affords the latter a conformation with effective C-s symmetry-indeed, the entire molecule is effectively minor-symmetric. The weighted average B-11 chemical shift of 2 is delta + 8.18 ppm, ca. 16 ppm to high frequency of that of 1. By H-1 and C-13{H-1} NMR spectroscopy it appears that the phenyl substituents of 2 spin at room temperature, but that the [9]aneS(3) ligand does not.
Inorganic Chemistry, Vol.35, No.16, 4548-4554, 1996
Mixed Sandwich Carborane/Thiamacrocycle Compounds - Synthesis and Characterization of 1-pH-3,3,3-(9)Anes(3)-Kappa(3)-S,S’,S"-3,1,2-Closo-Ruc2B9H10 and 1,2-pH(2)-3,3,3-(9)Anes(3)-Kappa(3)-S,S’,S"3,1,2-Pseudocloso-Ruc2B9H9
The reactions between [Ru([9]aneS(3))(MeCN)(3)][CF3SO3](2), a useful source of the [Ru{[9]aneS(3)-kappa(3)-S,S’,S-"}](2+) fragment dication, and [Tl][TlC(2)B(9)H(10)Ph] and [Tl][TlC(2)B(9)H(9)Ph(2)], respectively sources of the {C(2)B(9)H(10)Ph} and {C(2)B(9)H(9)Ph(2)}(2-) fragment dianions, have afforded 1-Ph-3,3,3-[9]aneS(3)-kappa(3)-S,S’,S-"-3,1,2-closo-RuC2B9H10, 1, and 1,2-Ph(2)-3,3,3-[9]aneS(3)-kappa(3)-S,S’,S-"-3,1,2-pseudocloso-RuC2B9H9, 2, the first reported examples of mixed thiamacrocyle/carborane compounds. Compounds 1 and 2 have been characterized by multinuclear (H-1, B-11{H-1}, and C-13{H-1}) NMR spectroscopy, and by single-crystal X-ray diffraction studies. Compound 1 [space group
Keywords:(9)ANES3 = 1;4;7-TRITHIACYCLONONANE;CROWN THIOETHER CHEMISTRY;MOLECULAR-STRUCTURES;MACROCYCLIC COMPLEXES;CRYSTAL-STRUCTURE;CARBAMETALLABORANES;RUTHENIUM