Neutral bi- and tripodal ligands of the type PhxP(L)3−x (x=1 (for 1), 0 (for 2); L=N-methylbenzamidyl (La, 1a, 2a), phthalimidyl (Lb, 1b, 2b), 2-pyridyloxy (Lc, 1c, 2c)) have been synthesized to act as P,O (1a, 1b, 2a, 2b) or P,N (1c, 2c) chelating ligands in the ruthenium coordination sphere. Reactions of the ruthenium source [RuCl2(PPh3)3] with 1a,b,c and 2b,cresult in the formation of all-cis bis-chelate complexes [RuCl2(PPh3)κ-P,O,O- or κ-P,N,N-(PhxP(L)3−x)] 3a,b,c (x=1) and 4b,c (x=0), respectively. Surprisingly, during the reaction of [RuCl2(PPh3)3] with 2a a P–N bond cleavage in favor of PO bond formation takes place with formation of complex 5a [RuCl(PPh3)2κ-P,O,O-(OP(La)2)]. Treatment of the reaction mixture with TlPF6 afforded the phosphonium salt 6 [Ph3P(Ph)CNMe]PF6. Attempts to form similar compounds to 5a with Lb or Lc (driven by chloride abstraction upon addition of TlPF6) only afforded the cationic complexes of the type [RuCl(PPh3)2κ-P,O,O- or κ-P,N,N-(P(L)3)]PF6 (L=Lb (7b), Lc (7c)). All isolated compounds were characterized with multi-nuclear NMR spectroscopy, single-crystal X-ray diffraction (except 4c) and elemental analysis.