TY - JOUR
T1 - Synthetic and structural studies on copper 1H-[1,10]-phenanthrolin-2-one coordination complexes: isolation of a novel intermediate during 1,10 Phenanthroline hydroxylation
AU - Szpakolski, Katherine B
AU - Latham, Kay
AU - Rix, C J
AU - White, Johnathan M
AU - Moubaraki, Boujemaa
AU - Murray, Keith Spencer
PY - 2010
Y1 - 2010
N2 - The synthesis and crystal Structure elucidation of a novel dinuclear heteroleptic copper(II) complex has led to an alternative mechanism in the formation of covalent hydrates. During further studies on the synthesis and properties of [Cu-2(ophen)(2)] (1), a dinuclear complex of copper(l) with 1H-[1,10]-phenanthrolin-2-one (Hophen), two intermediates/alternative products 2 and 3 were isolated. The dinuclear, antiferromagnetic complex [Cu-2(ophen)(2)(phen)(2)]center dot(NO3)(2)center dot 9H(2)O (3, phen=1,10-phenanthroline) contains two five-coordinate copper(II) ions, both with trigonal-bipyramidal coordination, which are bridged together through deprotonated hydroxyl groups with a Cu-Cu non-bonding distance of 3.100 angstrom. Complex [Cu(phen)(2)(H2O)]center dot-(NO3)(2) (2) is a polymorph of a previously reported material. The occurrence of 2 and 3 has led us to propose a variation to the Gillard mechanism for the formation of covalent hydrates in bidentate N-heterocycles in which the attacking nucleophile may be the deprotonated form of 2, [Cu(phen)(2)(OH)](-), rather than free OH-.
AB - The synthesis and crystal Structure elucidation of a novel dinuclear heteroleptic copper(II) complex has led to an alternative mechanism in the formation of covalent hydrates. During further studies on the synthesis and properties of [Cu-2(ophen)(2)] (1), a dinuclear complex of copper(l) with 1H-[1,10]-phenanthrolin-2-one (Hophen), two intermediates/alternative products 2 and 3 were isolated. The dinuclear, antiferromagnetic complex [Cu-2(ophen)(2)(phen)(2)]center dot(NO3)(2)center dot 9H(2)O (3, phen=1,10-phenanthroline) contains two five-coordinate copper(II) ions, both with trigonal-bipyramidal coordination, which are bridged together through deprotonated hydroxyl groups with a Cu-Cu non-bonding distance of 3.100 angstrom. Complex [Cu(phen)(2)(H2O)]center dot-(NO3)(2) (2) is a polymorph of a previously reported material. The occurrence of 2 and 3 has led us to propose a variation to the Gillard mechanism for the formation of covalent hydrates in bidentate N-heterocycles in which the attacking nucleophile may be the deprotonated form of 2, [Cu(phen)(2)(OH)](-), rather than free OH-.
UR - http://onlinelibrary.wiley.com.ezproxy.lib.monash.edu.au/doi/10.1002/chem.200901720/pdf
U2 - 10.1002/chem.200901720
DO - 10.1002/chem.200901720
M3 - Article
SN - 0947-6539
VL - 16
SP - 1691
EP - 1696
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 5
ER -