Reaction of the trinuclear cluster cation [Pd3(µ3-CO)(µ-dppm)3]2+[dppm = bis(diphenylphosphino)-methane] with excess xylyl isocyanide, 2,6-Me2C6H3NC, led to cleavage giving the binuclear palladium(I) complex cation [Pd2(CNC6H3Me2-2,6)2(µ-dppm)2]2+, and unidentified palladium(0) species. The 2,6-Me2C6H3NC ligands in [Pd2(CNC6H3Me2-2,6)2(µ-dppm)2]2+ undergo rapid exchange with excess 2,6-Me2C6H3NC and, at low temperature, an adduct is formed and identified spectroscopically as [Pd2(CNC6H3Me2-2,6)2(µ-CNC6H3Me2-2,6)(µ-dppm)2]2+. A dppm ligand of [Pd2(CNC6H3Me2-2,6)2(µ-dppm)2]2+ is deprotonated and oxidized in the presence of an excess of dppm and oxygen to give [Pd2(CNC6H3Me2-2,6)2{µ-Ph2PCHPPh2(O)-C,P}(µ-dppm)]+, which has been characterized by a structure determination {crystal data for the [PF6]–·Me2CO salt: triclinic, space group P, a= 14.523(2), b= 22.448(4), c= 12.203(3)A, α= 95.52(2), β= 110.98(2), γ= 108.21(1)°, Z= 2, R= 0.0563, R′= 0.0574}. Complex [Pd2(CNC6H3Me2-2,6)2(µ-dppm)2]2+ can react with the palladium(0) species, which is formed in the initial cluster cleavage reaction, by formal addition of Pd(CNC6H3Me2-2,6)2 to give the trinuclear A-frame cluster complex [Pd2(CNC6H3Me2-2,6)2{µ-Pd(CNC6H3Me2-2,6)2}(µ-dppm)2]2+, thus completing the fragmentation and reassembly of trinuclear clusters. This complex has been characterized by a structure determination {crystal data for the 2[PF6]–·0.5Me2CO salt: orthorhombic, space group P212121, a= 21.810(3), b= 21.879(4), c= 18.274(5)A, Z= 4, R= 0.0566, R′= 0.0632}; in solution, it slowly loses Pd(CNC6H3Me2-2,6)2 to reform [Pd2(CNC6H3Me2-2,6)2(µ-dppm)2]2+