Reaction of [(eta(5)-C5Me5)Ru(OMe)](2) (2) With HP(O)(OR)(2) gave the novel tripod ligands H-2(eta(5)-C5Me5)Ru{PO(OR)(2)}(3) (R = Me, Et, Pr-i, H(2)1). H-2(eta(5)-C5Me5)Ru{PO(Ph-2)}(3) was formed with HP(O)Ph-2. [(eta(5)-C5Me5)RuCl2](2) (3) with NaP(O)(OEt)(2) similarly gave Na-2(eta(5)-C5Me5)Ru{PO(OEt)(2)}(3) (Na(2)1; Na2L). Either the hydrogen form or the sodium salt was reacted with main group and transition metal halides to yield complexes [ML2](n-) (M = Si-IV, Ti-IV, Nb-IV, n = 0; Co-II, n = 2; Cr-III, Fe-III, n = 1), or complexes of the form LMX with MX = BPh, VO. Reaction of Na-2(eta(5)-C5Me5)Ru{PO(Ph-2)}(3) With TiCl4 gave intermediately [LTiCl2](2) which readily hydrolyzed on chromatography over Al2O3 to trinuclear (LTiO)(3)(mu(3)-O)H-2. The latter was characterized by X-ray structure analysis. It crystallizes in the cubic space group Pa3 (No. 205), z = 8, a = 30.83(1) Angstrom, V = 29300(30) Angstrom(3). From the reaction of Na(2)1 and 3 under appropriate conditions, the mixed valence complex LRu(eta(5)-C5Me5) (4) was isolated. Compounds were characterized by spectroscopy and electrochemistry. From absorption spectra of the Co-II and the Cr-III complex ligand field parameters Delta(o) = 902 and 1450 cm(-1), respectively, were derived, placing 1 near F- in the spectrochemical series.