The reactions of the mononuclear cyclodiphosphazane complexes, cis-[Mo(CO)₄{cis-[PhNP(OR)]₂}₂] with [Mo(CO)₄(nbd)](nbd = norbornadiene), [Mo(CO)₄(NHC₅H₁₀)₂] or [MCl₂(cod)](cod = cycloocta-1,5-diene) afforded the homobimetallic complexes, [Mo₂(CO)₈{µ-cis-[PhNP(OR)]₂}₂](R = C₆H₄Me-p5 or CH₂CF₃6) or the heterobimetallic complexes, [Mo(CO)₄{µ-cis-[PhNP(OR)]₂}₂MCl₂](R = C₆H₄Me-p; M = Pd 7 or Pt 8). In all the above complexes, the two metal moieties are bridged by two cyclodiphosphazane ligands. The reactions of the mononuclear complexes, cis-[M(CO)₄(A){cis-[PhNP(OC₆H₄Me-p)]₂}] with [M′Cl₂(cod)] afforded the trinuclear complexes, cis-[M′Cl₂[M(CO)₄(A){cis-[PhNP(OC₆H₄Me-p)]₂}]₂](M′= Pd, M = Mo, A = P(OMe)₃10; M′= Pt, M = Mo, A = P(OMe)₃11; M′= Pd, M = W, A = NHC₅H₁₀12; M′= Pt, M = W, A = NHC₅H₁₀13). The structure of the complex 5 has been determined by single-crystal X-ray crystallography.