1-Ph-3,3,3-[9]aneS3-κ(3)-S,S',S''-3,1,2-closo-RuC2B9H10 | 178767-29-8

• 英文名称: 1-Ph-3,3,3-[9]aneS3-κ(3)-S,S',S''-3,1,2-closo-RuC2B9H10
• CAS: 178767-29-8
• 化学式: C₁₄H₂₇B₉RuS₃
• 分子量: 489.935
• InChiKey: KHPRMUIXLSYIFB-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  Tl2[7-Ph-8-Me-7,8-nido-C2B9H9] 、 以 甲醇 为溶剂， 以56%的产率得到1-Ph-3,3,3-[9]aneS3-κ(3)-S,S',S''-3,1,2-closo-RuC2B9H10
  参考文献：
  名称：

  Mixed Sandwich Carborane/Thiamacrocycle Compounds. Synthesis and Characterization of 1-Ph-3,3,3-[9]aneS₃-κ³-S,S‘,S‘‘-3,1,2-closo-RuC₂B₉H₁₀ and 1,2-Ph₂-3,3,3-[9]aneS₃-κ³-S,S‘,S‘‘-3,1,2-pseudocloso-RuC₂B₉H₉^,

  摘要：

  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 , 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.

  DOI：

  10.1021/ic9601899