Synthesis, reactivity studies, structural aspects, and solution behavior of half sandwich ruthenium(II) N,N',N''-triarylguanidinate complexes.

[(η6-C10H14)RuCl(μ-Cl)]2 (η6-C10H14 = η6-p-cymene) was subjected to a bridge-splitting reaction with N,N′,N″-triarylguanidines, (ArNH)2C═NAr, in toluene at ambient temperature to afford [(η6-C10H14)RuCl{κ2(N,N′)((ArN)2C–N(H)Ar)}] (Ar = C6H4Me–4 (1), C6H4(OMe)–2 (2), C6H4Me–2 (3), and C6H3Me2–2,4 (4)) in high yield with a view aimed at understanding the influence of substituent(s) on the aryl rings of the guanidine upon the solid-state structure, solution behavior, and reactivity pattern of the products. Complexes 1–3 upon reaction with NaN3 in ethanol at ambient temperature afforded [(η6-C10H14)RuN3{κ2(N,N′)((ArN)2C–N(H)Ar)}] (Ar = C6H4Me–4 (5), C6H4(OMe)–2 (6), and C6H4Me–2 (7)) in high yield. [3 + 2] cycloaddition reaction of 5–7 with RO(O)C–C≡C–C(O)OR (R = Et (DEAD) and Me (DMAD)) (diethylacetylenedicarboxylate, DEAD; dimethylacetylenedicarboxylate, DMAD) in CH2Cl2 at ambient temperature afforded [(η6-C10H14)Ru{N3C2(C(O)OR)2}{κ2(N,N′)((ArN)2C–N(H)Ar)}]·xH2O (x = 1, R = Et, Ar = C6H4Me–4 (8·H2O); x = 0,...