Complex [RuCl{κ 3 (N,N,N)-Tp}(PPh 3 )(PTA)] (κ 3 (N,N,N)-Tp=hydridotris(pyrazolyl)borate) containing the water-soluble phosphane 1,3,5-triaza-7-phosphatricyclo[3.3.1.1 3,7 ]decane (PTA) reacts with terminal alkynes producing to the corresponding neutral alkynyl complexes [Ru(CCR){κ 3 (N,N,N)-Tp}(PPh 3 )(PTA)] (R=Ph (1a), n Bu (1b), 1-cyclopentenyl (1c), p-methoxyphenyl (1d), 6-methoxynaft-2-yl (1e)). When halide is extracted from complex [RuCl{κ 3 (N,N,N)-Tp}(PPh 3 )(PTA)] followed by treatment with propargyl alcohols, the corresponding allenylidene complexes [Ru{κ 3 (N,N,N)-Tp}(PPh 3 )(PTA)(CCCPh 2 )][X] (X=PF 6 (2a), CF 3 SO 3 (2b)) and [Ru{κ 3 (N,N,N)-Tp}(PPh 3 )(PTA)(CCCC 12 H 8 )][PF 6 ] (3) result. Electrophilic attack on the complexes thus obtained leads chemoselectively to the alkynyl complexes [Ru(CCR){κ 3 (N,N,N)-Tp}(PPh 3 )(1-CH 3 -PTA)][CF 3 SO 3 ] (R=Ph (4a), n Bu (4b), and 1-cyclopentenyl (4c)) and to the dicationic allenylidene complexes [Ru{κ 3 (N,N,N)-Tp}(PPh 3 )(1-H-PTA)(CCCC 12 H 8 )][PF 6 ] 2 (5) and [Ru{κ 3 (N,N,N)-Tp}(PPh 3 )(1-CH 3 -PTA)(CCCPh 2 )][CF 3 SO 3 ] 2 (6).