Reaction of RuCl2(PPh3)(3) with LiNN' (NN' = 2-[(2,6-diisopropylphenyl)imino]pyrrolide) affords a single product, with the empirical formula RuCl[(2,6-(Pr2C6H3)-Pr-i)N=CHC4H3N](PPh3)(2). We identify this species as a sigma-pyrrolato complex, [Ru(NN')(PPh3)(2)](2)(mu-Cl)(2) (3b), rather than mononuclear RuCl(NN')(PPh3)(2) (3a), on the basis of detailed 1D and 2D NMR characterization in solution and in the solid state. Retention of the chelating, sigma-bound iminopyrrolato unit within 3b, despite the presence of labile ( dative) chloride and PPh3 donors, indicates that the chelate effect is sufficient to inhibit sigma -> pi isomerization of 3b to a piano-stool, pi-pyrrolato structure. 2D COSY, SECSY, and J-resolved solid-state P-31 NMR experiments confirm that the PPh3 ligands on each metal center are magnetically and crystallographically inequivalent, and P-31 CP/MAS NMR experiments reveal the largest Ru-99-P-31 spin-spin coupling constant ((1)J(Ru-99, P-31) 244 +/- 20 Hz) yet measured. Finally, P-31 dipolar-chemical shift spectroscopy is applied to determine benchmark phosphorus chemical shift tensors for phosphine ligands in hexacoordinate ruthenium complexes.