Treatment of Ru(PPh3)(3)Cl-2 with K(tpip) (tpip(-) = [N(Ph2PO)(2)](-)) afforded Ru(tpip)(PPh3)(2)Cl (1), which reacted with 4-t-Bu-C6H4CN, SO2(g), and NH3(g) to give Ru(tpip)(PPh3)(2)Cl(4-t-BuC6H4CN) (2), Ru(tpip)(PPh3)(2)Cl(SO2) (3), and fac-[Ru(NH3)(3)(PPh3)(2)Cl][tpip] (4), respectively. Reaction of [Ru(CO)(2)Cl-2], with K(tpip) in refluxing tetrahydrofuran (THF) led to isolation of the K/Ru bimetallic compound K2Ru2(tPiP)(4)(CO)(4)Cl-2 (5). Photolysis of cis-Ru(tpip)(2)(NO)Cl in MeCN and wet CH2Cl2 afforded cis-Ru(tpip)(2)(MeCN)Cl (6) and cis-Ru(tpip)(2)(H2O)Cl (7), respectively. Refluxing 6 in neat THF yielded Ru(tpip)(2)(THF)Cl (8). Treatment of Ru(CHR)Cl-2(PCy3)(2) (Cy = cyclohexyl) with [Ag(tpip)](4) afforded cis-Ru(tpip)(2)(CHR)(PCy3) [R = Ph (9), OEt (10)]. Complex 9 is capable of catalyzing oxidation of alcohols and olefins with N-methylmorpholine N-oxide and iodosylbenzene, respectively. The crystal structures of 2-7 and 9 were determined.