Mixed Sandwich Carborane/Thiamacrocycle Compounds. Synthesis and Characterization of 1-Ph-33,3-[9]aneS3-K 3-S,S′,S″-3,1,2-closo-RuC2B9H 10 and 1,2-Ph2-3,3,3-[9]aneS3-K 3-S,S′,S″,3,1,2-pseudocloso-RuC2B 9H9

Alan J. Welch, Andrew S. Weller

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25 Citations (Scopus)

Abstract

The reactions between [Ru([9]aneS3)(MeCN)3][CF3SO3] 2, a useful source of the [Ru{[9]aneS3-k3-S,S',S?}]2+ fragment dication, and [Tl][TlC2B9H10Ph] and [Tl][TlC2B9H9Ph2], respectively sources of the {C2B9H10Ph}2- and {C2B9H9Ph2}2- fragment dianions, have afforded 1-Ph-3,3,3-[9]aneS3-k 3-S,S',S?-3,1,2-closo-RuC2B9H 10, 1, and 1,2-Ph2-3,3,3-[9]aneS3-k 3-S,S',S?-3,1,2-pseudocloso-RuC2B 9H9, 2, the first reported examples of mixed thiamacrocyle/carborane compounds. Compounds 1 and 2 have been characterized by multinuclear (1H, 11B-{1H}, and 13C{1H}) WAR spectroscopy, and by single-crystal X-ray diffraction studies. Compound 1 [space group P1¯, a = 10.3552(7) Å, b = 13.7960(18) Å, c = 15.9795(13) Å, a = 68.227(7)°, ß= 82.983(5)°, ? = 82.496(7)°, R = 0.0377 for 5893 observed data] is a closo metal carborane, based on an icosahedron, in which the [9]andS3 ligand has effective C3, 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) Å, b = 16.907(3) Å, c = 17.757(4) Å, 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) Å and Ru(3)?B(6) 2.960(6) Å, as a consequence of intramolecular crowding between the phenyl cage substituents. Phenyl/thiamacrocycle intramolecular crowding affords the latter a conformation with effective Cs symmetry-indeed, the entire molecule is effectively mirror-symmetric. The weighted average 11B chemical shift of 2 is d +8.18 ppm, ca. 16 ppm to high frequency of that of 1. By 1H and 13C{1H} NMR spectroscopy it appears that the phenyl substituents of 2 spin at room temperature, but that the [9]aneS3 ligand does not.

Original languageEnglish
Pages (from-to)4548-4554
Number of pages7
JournalInorganic Chemistry
Volume35
Issue number16
Publication statusPublished - 1996

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