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Reactions of Gaseous Nitric Oxide with Anionic Ruthenium Carbide Carbonyl Clusters

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journal contribution
posted on 09.01.1996, 00:00 by Teiji Chihara, Koushi Sawamura, Hidenori Ikezawa, Haruo Ogawa, Yasuo Wakatsuki
Gaseous nitric oxide reacted with the dianionic hexanuclear ruthenium carbide cluster [PPN]2[Ru6C(CO)16] (PPN = (PPh3)2N) to give the monoanionic nitrosyl complex [PPN][Ru6C(CO)15(NO)] (2) in good yield. On further reaction with gaseous NO, 2 gave a neutral pentanuclear complex with NO and NO2 ligands, Ru5C(CO)14(NO)(NO2), the structure of which was confirmed by X-ray analysis of the phosphine derivative Ru5C(CO)13(PPh3)(NO)(NO2) (4). A monoanionic allyl derivative of the hexanuclear ruthenium cluster, [PPN][Ru6C(CO)15(C3H5)], reacted with NO to give neutral hexa- and pentanuclear allyl complexes with NO (and NO2) ligands, Ru6C(CO)14(C3H5)(NO) (6) and Ru5C(CO)11(C3H5)(NO)2(NO2) (7). Addition of gaseous NO to 6 gave rise to another pentanuclear complex Ru5C(CO)13(C3H5)(NO2) (8) which did not react further with NO. The solid state structures of the new NO and NO2 complexes 4 and 6−8 are reported.