Abstract: We have established a new route for boron-rich ruthenaborane clusters utilizing [BH 3 ·THF] and a ruthenium precursor featuring chelating ligands. Salt elimination reactions between [K(C 5 H 4 NE)], (E = S; Se) and [RuCl 2 (PPh 3 ) 3 ], 1 afforded cis -[Ru(κ 2 - N,E -C 5 H 4 NE) 2 (PPh 3 ) 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(κ 2 - N,E -C 5 H 4 NE) 2 (dppe)] ( cis - 3a : E = S; cis - 3b : E = Se). Reactivity of cis -[Ru(κ 2 - N,E -C 5 H 4 NE) 2 (dppe)] ( cis - 3a - b ) with [BH 3 ·THF] under thermolytic conditions led to the formation of two isomeric nido -ruthenadecaboranes [7,7-(PPh 2 CH 2 ) 2 -7-E-3-N- nido -7-RuB 9 H 12 ] ( 4a : E = S; 4b : E = Se) and [6,6-(PPh 2 CH 2 ) 2 -6-E-7-N- nido -6-RuB 9 H 12 ] ( 5a : E = S; 5b : E = Se), in which ruthenium occupies the seventh and sixth cluster vertices, respectively. Additionally, 9-vertex nido -ruthenaborane, [2,2,-(PPh 2 CH 2 ) 2 -2-E-1-N- nido -2-RuB 8 H 11 ] ( 6a : E = S; 6b : E = Se), was also isolated. In contrast, the reactivity of [Ru(κ 2 - N,E -C 5 H 4 NE) 2 (PPh 3 ) 2 ] cis - 2a - b , with [BH 3 ·THF] or [BHCl 2 ·SMe 2 ], led to the formation of complexes fac -[Ru{κ 3 - H,E,E ′-(NXHBEBHXN)(EC 5 H 4 ) 2 }PPh 3 ] ( 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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