In the presence of excess of triphenylphosphine, RuCl(PPh) binds a fourth phosphine to give black RuCl(PPh). The triphenylphosphine ligands in both the tris(phosphine) and tetrakis(phosphine) complexes are readily substituted by other ligands. The tetrakis(phosphine) complex is a precursor to the Grubbs catalysts.
Dichlorotris(triphenylphosphine)ruthenium(II) reacts with hydrogen in the presence of base to give the purple-colored monohydride HRuCl(PPh).
:RuCl(PPh) + H + NEt → HRuCl(PPh) + [HNEt]Cl
Dichlorotris(triphenylphosphine)ruthenium(II) reacts with carbon monoxide to produce the all trans isomer of dichloro(dicarbonyl)bis(triphenylphosphine)ruthenium(II).
:RuCl(PPh) + 2 CO → trans,trans,trans-RuCl(CO)(PPh) + PPh
This kinetic product isomerizes to the cis adduct during recrystallization. trans-RuCl(dppe) forms upon treating RuCl(PPh) with dppe.
:RuCl(PPh) + 2 dppe → RuCl(dppe) + 3 PPh
RuCl(PPh) catalyzes the decomposition of formic acid into carbon dioxide and hydrogen gas in the presence of an amine.  Since carbon dioxide can be trapped and hydrogenated on an industrial scale, formic acid represents a potential storage and transportation medium.