Pulled molecular strings and stacked molecular decks: Chelate-ring formation vs. metal-metal bridging in dicopper(I) complexes of 2,2'-bipyrimidine with diphosphine ligands of variable polymethylene chain length

, , and . Chemistry - A European Journal 2 (4): 446--451 (1996)


The self-assembly reaction between bischelating 2,2'-bipyrimidine (bpym), metallic Cu, Cu2+, and two equiv. of bidentate Ph2P(CH2)nPPh2 produces crystallog. characterized dinuclear complexes with a CuI(m-bpym)CuI2+ core and chelating (n = 5) or bridging diphosphine ligands (n = 6, 8). The bridging type may be designated as inverse cryptate arrangements. The structural data of the solids and the spectroscopic results for the dissolved species indicate a strained configuration in the case of (m-bpym)Cu2μ-Ph2P(CH2)nPPh222+ with n = 6. Once the polymethylene chain length is reduced one notch further to n = 5, the diphosphines can no longer bridge but help to form eight-membered chelate rings. In this complex there is a distortion towards a trigonal-pyramidal coordination geometry at the Cu(I) centers, which is supported by the formation of an org. sandwich arrangement between the central bpym acceptor and two phosphino Ph rings. on SciFinder(R)

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