SYNTHESIS, CHARACTERIZATION, AND X-RAY CRYSTAL-STRUCTURE OF [RU(NO2)(PME3)2(TRPY)](CLO4)

The complex trans-[Ru(NO2)(PMe3)2(trpy)](ClO4) (where trpy = 2,2′:6′,2″-terpyridine and PMe3 = trimethylphosphine), has been prepared by using a five-step synthesis, starting from RuCl3•3H2O, with a total overall yield of 27%. In addition, a three-step synthesis for the formation of trans-[Ru(NO2)(PMe3)2(trpy)](ClO4) was developed, where an increase in the total overall yield from 27% to 71% was observed. Characterization of trans-[Ru(NO2)(PMe3)2(trpy)](ClO4) was accomplished through UV-visible, IR, and 1H and 13C NMR spectroscopies, cyclic voltammetry, coulometry, and elemental analysis. An X-ray crystallographic structural determination was also performed, where trans-[Ru(NO2)(PMe3)2(trpy)](ClO4) crystallized in the monoclinic space group P21/c with cell parameters of a = 16.102 (11) Å, b = 10.365 (7) Å, c = 16.788 (12) Å, β = 108.23 (5)°, and Z = 4. Final discrepancy indices were RF = 7.1% and RwF = 6.4% for all 3169 nonzero data and RF = 4.2% and Rwf = 5.1% for those 2186 reflections with |Fo| > 6σ(|Fo|). The ruthenium to nitrogen bond distances were Ru-N(nitro) = 2.074 (6) Å and Ru-N(trpy) = 2.088 (6), 1.985 (5), and 2.093 (7) Å. The ruthenium to phosphorus bond distances were Ru-P = 2.361 (3) and 2.368 (3) Å. © 1990, American Chemical Society. All rights reserved.