Three symmetrical N,N′,N′′-triarylguanidinatoruthenium(II) complexes, [(η 6 -p-cymene)RuCl{κ 2 (N,N′)((ArN) 2 C-N(H)Ar)}] (Ar = 2-(CF 3 )C 6 H 4 (1), 4-(CF 3 )C 6 H 4 (2) and 3,5-(CF 3 ) 2 C 6 H 3 (3)) were isolated in good yields. The reaction of 3 with NaOAc, NaN 3 and KSCN afforded [(η 6 -p-cymene)RuX{κ 2 (N,N′)((ArN) 2 C-N(H)Ar)}] (X = OAc (4), N 3 (5) and an admixture of SCN (6) and NCS (7)) respectively in very good yields. On the other hand, metathesis reaction of 3 with AgSbF 6 in the presence of MeCN afforded [(η 6 -pcymene)Ru(MeCN){κ 2 (N,N′)((ArN) 2 C-N(H)Ar)}][SbF 6 ] (8) in good yield. Complex 5 upon treatment with diethylacetylenedicarboxylate and bis(diphenylphosphanyl)acetylene separately afforded [a]