摘要 : The reaction of [CpRuCl-ACHTUNGTRENUNG(PPh3)2] (Cp=cyclopentadienyl) and [CpRuClACHTUNGTRENUNG(dppe)] (dppe=Ph2PCH2CH2PPh2) with bis- and trisphosphine ligands 1,4-(Ph2PCC)2C6H4 (1) and 1,3,5-(Ph2PC C)3C6H3 (2), prepared by Ni-cat... 展开 The reaction of [CpRuCl-ACHTUNGTRENUNG(PPh3)2] (Cp=cyclopentadienyl) and [CpRuClACHTUNGTRENUNG(dppe)] (dppe=Ph2PCH2CH2PPh2) with bis- and trisphosphine ligands 1,4-(Ph2PCC)2C6H4 (1) and 1,3,5-(Ph2PC C)3C6H3 (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,[{CpRuClACHTUNGTRENUNG(PPh3)}2ACHTUNGTRENUNG(m-dppab)] (3)and [{CpRuACHTUNGTRENUNG(dppe)}2ACHTUNGTRENUNG(m-dppab)]ACHTUNGTRENUNGPF6)2 (4),and the mononuclear complex [CpRuClACHTUNGTRENUNG(PPh3)CHTUNGTRENUNG(h1-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- ACHTUNGTRENUNG(PPh3)}3ACHTUNGTRENUNG(m3-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 [{CpRuClACHTUNGTRENUNG(mdppab)} 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- ACHTUNGTRENUNG(PPh3)] were obtained, that is, the dinuclear complex [{CpRuACHTUNGTRENUNG(PPh3)ACHTUNGTRENUNG(mdppab)} 2]ACHTUNGTRENUNG(PF6)2 (8) and the tetranuclear square [{CpRuACHTUNGTRENUNG(PPh3)ACHTUNGTRENUNG(mdppab)} 4]ACHTUNGTRENUNG(PF6)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. 收起