Cyclopentadienyl ruthenium(II) complexes with bridging alkynylphosphine ligands: synthesis and electrochemical studies.

The reaction of [CpRuCl(PPh(3))(2)] (Cp = cyclopentadienyl) and [CpRuCl(dppe)] (dppe = Ph(2)PCH(2)CH(2)PPh(2)) with bis- and tris-phosphine ligands 1,4-(Ph(2)PC[triple bond]C)(2)C(6)H(4) (1) and 1,3,5-(Ph(2)PC[triple bond]C)(3)C(6)H(3) (2), prepared by Ni-catalysed cross-coupling reactions between terminal alkynes and diphenylchlorophosphine, has been investigated. Using metal-directed self-assembly methodologies, two linear bimetallic complexes, [{CpRuCl(PPh(3))}(2)(mu-dppab)] (3) and {CpRu(dppe)}(2)(mu-dppab)(2) (4), and the mononuclear complex [CpRuCl(PPh(3))(eta(1)-dppab)] (6), which contains a "dangling arm" ligand, were prepared (dppab =1,4-bis[(diphenylphosphino)ethynyl]benzene). Moreover, by using the triphosphine 1,3,5-tris[(diphenylphosphino)ethynyl]benzene (tppab), the trimetallic [{CpRuCl(PPh(3))}(3)(mu(3)-tppab)] (5) species was synthesised, which is the first example of a chiral-at-ruthenium complex containing three different stereogenic centres. Besides these open-chain complexes, the neutral cyclic species [{CpRuCl(mu-dppab)}(2)] (7) was also obtained under different experimental conditions. The coordination chemistry of such systems towards supramolecular assemblies was tested by reaction of the bimetallic precursor 3 with additional equivalents of ligand 2. Two rigid macrocycles based on cis coordination of dppab to [CpRu(PPh(3))] were obtained, that is, the dinuclear complex {CpRu(PPh(3))(mu-dppab)}(2)(2) (8) and the tetranuclear square {CpRu(PPh(3))(mu-dppab)}(4)(4) (9). The solid-state structures of 7 and 8 have been determined by X-ray diffraction analysis and show a different arrangement of the two parallel dppab ligands. All compounds were characterised by various methods including ESIMS, electrochemistry and by X-band ESR spectroscopy in the case of the electrogenerated paramagnetic species.