Synthesis and Characterization of Novel Monocarbollide e xo-closo-(π-Arene)biruthenacarboranes [(PPh3) m ClRu(η6-C6H5R)Ru‘CB10H11 - n (OMe) n ] (where R = H, m = 2, n = 1; R = μ-PPh2, m = 1, n = 0, 1)

• Published in: Inorganic chemistry 2004-10, Vol.43 (20), p.6228-6237
• Main Authors: Pisareva, Irina V, Konoplev, Vitalii E, Petrovskii, Pavel V, Vorontsov, Evgenii V, Dolgushin, Fedor M, Yanovsky, Alexandr I, Chizhevsky, Igor T
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic0497883

The monocarbon carborane [Cs][nido-7-CB10H13] reacts with the 16-electron [RuCl2(PPh3)3] in a solution of benzene/methanol in the presence of N,N,N ‘,N ‘-tetramethylnaphthalene-1,8-diamine as the base to give a series of 12-vertex monocarbon arene-biruthenacarborane complexes of two types:  [closo-2-{7,11-exo-RuClPPh3(μ,η6-C6H5PPh2)}-7,11-(μ-H)2-2,1-RuCB10H8R] (5, R = H; 6, R = 6-MeO; 7, R = 3-MeO) and [closo-2-(η6-C6H6)-10,11,12-{exo-RuCl(PPh3)2}-10,11,12-(μ-H)3-2,1-RuCB10H7R1] (8a, R1 = 6-MeO; 8b, R1 = 3-MeO, inseparable mixture of isomers) along with trace amounts of 10-vertex mononuclear hypercloso/isocloso-type complexes [2,2-(PPh3)2-2-H-3,9-(MeO)2-2,1-RuCB8H7] (9) and [2,5-(Ph3P)-2-Cl-2-H-3,9-(MeO)2-2,1-RuCB8H6] (10). Binuclear ruthenacarborane clusters of both series were characterized by a combination of analytical and multinuclear NMR spectroscopic data and by single-crystal X-ray diffraction studies of three selected complexes, 6−8. In solution, isomers 8a,b have been shown to undergo the isomerization process through the scrambling of the exo-{RuCl(PPh3)2} fragment about two adjacent triangular cage boron faces B(7)B(11)B(12) and B(8)B(9)B(12).