Synthetic and Structural Studies on Copper 1 H‐[1,10]‐Phenanthrolin‐2‐one Coordination Complexes: Isolation of a Novel Intermediate During 1,10‐Phenanthroline Hydroxylation |
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| Authors: | Katherine B. Szpakolski Kay Latham Dr. Colin J. Rix Jonathan M. White Prof. Boujemaa Moubaraki Dr. Keith S. Murray Prof. |
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| Affiliation: | 1. School of Applied Sciences, Applied Chemistry, RMIT University, Melbourne, VIC 3001 (Australia), Fax: (+61)?39925‐3747;2. School of Chemistry, University of Melbourne, Melbourne, VIC 3011 (Australia);3. School of Chemistry, Monash University, Clayton, VIC 3800 (Australia) |
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| Abstract: | 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 [Cu2(ophen)2] ( 1 ), a dinuclear complex of copper(I) with 1 H‐[1,10]‐phenanthrolin‐2‐one (Hophen), two intermediates/alternative products 2 and 3 were isolated. The dinuclear, antiferromagnetic complex [Cu2(ophen)2(phen)2] ? (NO3)2 ? 9H2O ( 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 Å. Complex [Cu(phen)2(H2O)] ? (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?. |
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| Keywords: | copper hydroxylation nitrogen heterocycles reaction mechanisms structure elucidation |
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