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 R_F = 7.1% and R_wF = 6.4% for all 3169 nonzero data and R_F = 4.2% and R_wf = 5.1% for those 2186 reflections with |F_o| > 6σ(|F_o|). 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.