REACTIONS OF GASEOUS NITRIC-OXIDE WITH ANIONIC RUTHENIUM CARBIDE CARBONYL CLUSTERS

Gaseous nitric oxide reacted with the dianionic hexanuclear ruthenium carbide cluster [PPN](2)[Ru6C(CO)(16)] (PPN = (PPh(3))(2)N) to give th e monoanionic nitrosyl complex [PPN][Ru6C(CO)(15)(NO)] (2) in good yie ld, 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)(PPh(3))(NO)(NO2) (4). A monoanionic allyl derivative of t he hexanuclear ruthenium cluster, [PPN][Ru6C(CO)(15)(C3H5)], reacted w ith NO to give neutral hexa- and pentanuclear allyl complexes with NO (and NO2) ligands, Ru6C(CO)14(C3H5)(NO) (6) and RU(5)C(CO)(11)(C3H5)(N o)(2)(NO2) (7). Addition of gaseous NO to 6 gave rise to another penta nuclear complex Ru5C(CO)(13)(C3H5)(NO2) (8) which did not react furthe r with NO. The solid state structures of the new NO and NO2 complexes 4 and 6-8 are reported.