740835-18-1Relevant articles and documents
Tetranuclear (borole)rhodium clusters with hydrido and methylthiolato ligands - Structures of [{Rh(C4H4BMe)}4(μ 3-H)(μ3-I)3] and of [{Rh(C4H 4BPh)}2(μ-SMe)(μ3-SMe)]2 (2 Rh-Rh)
Herberich, Gerhard E.,Eckenrath, Hartmut J.,Wagner, Trixie,Wang, Ruimin
, p. 1396 - 1401 (2004)
The heterocubanes [Rh(C4H4BR)(μ3-I)] 4 (1a: R = Ph; 1b: R = Me) can be hydrogenated in THF (suspension, 1 bar H2, 20 °C) to give the μ3-hydrido clusters [{Rh(C4H4BR)}4(μ3-H) (μ3-I)3] (2a,b). The structure of 2b consists of a Rh4(μ3-H)(μ3-I)3 core with idealized C3v symmetry and four capping η5-borole ligands. The Rh-Rh distances within the Rh3(μ3-H) cluster unit amount to 2.9448(6), 2.9647(6), and 2.9724(6) A; the μ3-H ligand is 0.064(5) A above the Rh3 plane with a mean Rh-H bond length of 1.83(5) A. The tris(acetonitrile) salts [Rh(C4H4BR)(NCMe)3]BF4 (4a,b) react with NaSMe to give the methylthiolato complexes [Rh(C4H 4BR)(SMe)]x (3a,b). In the crystal 3a possesses a centrosymmetric stepped-ladder structure [{Rh(C4H4BPh)} 2(μ3-SMe)]2 (2Rh-Rh) (3a-Rh4), with a Rh-Rh bond length of 2.9233(11) A. In solution a dissociation equilibrium is observed with a predominating dinuclear complex [Rh(C 4H4BPh)(μ-SMe)]2 (3a-Rh2); in pyridine a closely related solvate [Rh(py)(C4H4BPh)(μ- SMe)]2 (5) with a static Rh2(μ-SMe)2 core is formed. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinstein, Germany, 2004.
