Synthesis and Complexation Properties of the Anions (eta(5)-C(5)Me(5))Ru(PR(2)O)(3)(2)(-) as Ligands

Reaction of [(eta(5)-C(5)Me(5))Ru(OMe)](2) (2) with HP(O)(OR)(2) gave the novel tripod ligands H(2)(eta(5)-C(5)Me(5))Ru{PO(OR)(2)}(3) (R = Me, Et, (i)Pr, H(2)1). H(2)(eta(5)-C(5)Me(5))Ru{PO(Ph(2))}(3) was formed with HP(O)Ph(2). [(eta(5)-C(5)Me(5))RuCl(2)](2) (3) with NaP(O)(OEt)(2) similarly gave Na(2)(eta(5)-C(5)Me(5))Ru{PO(OEt)(2)}(3) (Na(2)1; Na(2)L). Either the hydrogen form or the sodium salt was reacted with main group and transition metal halides to yield complexes [ML(2)](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)-C(5)Me(5))Ru{PO(Ph(2))}(3) with TiCl(4) gave intermediately [LTiCl(2)](2) which readily hydrolyzed on chromatography over Al(2)O(3) to trinuclear (LTiO)(3)(&mgr;(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) Å, V = 29300(30) Å(3). From the reaction of Na(2)1 and 3 under appropriate conditions, the mixed valence complex LRu(eta(5)-C(5)Me(5)) (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.