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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Boron-Rich Metallaboranes from κ2-N,E-Chelated Ru Complexes (E = S or Se): A Direct Route to Ruthenaboranes
Asif Ahmad1, Urvashi Gupta1, Sundargopal Ghosh1
1Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India.
None:
We have established a new route for boron-rich ruthenaborane clusters utilizing [BH3·THF] and a ruthenium precursor featuring chelating ligands. Salt elimination reactions between [K(C5H4NE)], (E = S; Se) and [RuCl2(PPh3)3], 1 afforded cis-[Ru(κ2-N,E-C5H4NE)2(PPh3)2], cis-2a-b (cis-2a: E = S and cis-2b: E = Se). Following the ligand exchange reaction with the 1,2-bis (diphenylphosphino)ethane (dppe) ligand yielded cis-[Ru(κ2-N,E-C5H4NE)2(dppe)] (cis-3a: E = S; cis-3b: E = Se). Reactivity of cis-[Ru(κ2-N,E-C5H4NE)2(dppe)] (cis-3a-b) with [BH3·THF] under thermolytic conditions led to the formation of two isomeric nido-ruthenadecaboranes [7,7-(PPh2CH2)2-7-E-3-N-nido-7-RuB9H12] (4a: E = S; 4b: E = Se) and [6,6-(PPh2CH2)2-6-E-7-N-nido-6-RuB9H12] (5a: E = S; 5b: E = Se), in which ruthenium occupies the seventh and sixth cluster vertices, respectively. Additionally, 9-vertex nido-ruthenaborane, [2,2,-(PPh2CH2)2-2-E-1-N-nido-2-RuB8H11] (6a: E = S; 6b: E = Se), was also isolated. In contrast, the reactivity of [Ru(κ2-N,E-C5H4NE)2(PPh3)2] cis-2a-b, with [BH3·THF] or [BHCl2·SMe2], led to the formation of complexes fac-[Ru{κ3-H,E,E'-(NXHBEBHXN)(EC5H4)2}PPh3] (fac-7a: X = H, E = S; fac-7b: X = H, E = Se; fac-8a: X = Cl; E = S). All of the synthesized molecules have been thoroughly characterized using NMR spectroscopy, ESI-MS, and single-crystal X-ray diffraction studies for structural elucidation. Additionally, theoretical studies have provided insights into the bonding and electronic structures of these molecules.
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