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
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)
%0 Journal Article
%1 Schwach.1996
%A Schwach, Manuela
%A Hausen, H.-D.
%A Kaim, Wolfgang.
%D 1996
%J Chemistry - A European Journal
%K assembly;crystal bipyrimidine chain copper dinuclear dinuclear;ESR dinuclear;copper dinuclear;deck dinuclear;electrochem dinuclear;string diphosphine length mol redn reduced self structure
%N 4
%P 446--451
%R 10.1002/chem.19960020414
%T 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
%V 2
%X 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)
@article{Schwach.1996,
abstract = {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(\textgreek{m}-bpym)CuI]2+ 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 [(\textgreek{m}-bpym)Cu2{μ-Ph2P(CH2)nPPh2}2]2+ 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)]},
added-at = {2019-07-15T13:41:23.000+0200},
author = {Schwach, Manuela and Hausen, H.-D. and Kaim, Wolfgang.},
biburl = {https://puma.ub.uni-stuttgart.de/bibtex/224ef385d30ce4a85038824663d2025a3/b_schwederski},
doi = {10.1002/chem.19960020414},
interhash = {add13b464c067bedadd1a9076608e978},
intrahash = {24ef385d30ce4a85038824663d2025a3},
issn = {0947-6539},
journal = {Chemistry - A European Journal},
keywords = {assembly;crystal bipyrimidine chain copper dinuclear dinuclear;ESR dinuclear;copper dinuclear;deck dinuclear;electrochem dinuclear;string diphosphine length mol redn reduced self structure},
number = 4,
pages = {446--451},
timestamp = {2019-07-15T11:42:10.000+0200},
title = {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},
volume = 2,
year = 1996
}