Abstract
The salts [K(Q)][MH5(PiPr3)2] (1Os, 1Ru, Q = 18-crown-6; 2Os, 2Ru, Q = 1-aza-18-crown-6; 3Os, 3Ru, Q = 1,10-diaza-18-crown-6) were prepared by the reaction of OsH2Cl2(PiPr3)2 or RuCl3/2.5PiPr3 with KH in the presence of one of these crown ethers under an atmosphere of H2 and were characterized by NMR and infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The X-ray structures of 3Os and 3Ru indicate that short intermolecular proton−hydride interactions between the hydrides of the anion and the NH moieties of the cation cause the self-assembly of one-dimensional networks of pentagonal bipyramidal [MH5(PiPr3)2]- anions and [K(diaza-18-crown-6)]+ cations. The X-ray structures of 2Os and 2Ru indicate that these also form one-dimensional chains due to MH···HN and weak MH···HC interactions between the hydrides of the anions and the NH and methylene CH of the [K(aza-18-crown-6)]+ cation. The MH···HN distance is 1.7 A for both 2Os and 2Ru and 1.9 and 1.8 A for 3Os and 3Ru, respectivel...
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