Dinuclear Paddle-Wheel Copper(II) Carboxylates in the Catalytic Oxidation of Carboxylic Acids. Unusual Polymeric Chains Found in the Single-Crystal X-ray Structures of [Tetrakis(
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- 作者：Frank P. W. Agterberg ; Hajo A. J. Provó ; Kluit ; Willem L. Driessen ; Henk Oevering ; Wim Buijs ; Miles T. Lakin ; Anthony L. Spek ; and Jan Reedijk
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：September 24, 1997
- 年：1997
- 卷：36
- 期：20
- 页码：4321 - 4328
- 全文大小：229K
- 年卷期：v.36,no.20(September 24, 1997)
- ISSN：1520-510X
文摘
The X-ray structures and spectroscopic and magnetic properties of[tetrakis(
-1-phenylcyclopropane-1-carboxylato-O,O')bis(ethanol-O)dicopper(II)],1, andcatena-poly[[bis(-diphenylacetato-O:O')dicopper](3-diphenylacetato-1-O:2-O':1'-O')(3-diphenylacetato-1-O:2-O':2'-O')],2, two extended-chain copper(II) carboxylates withdinuclearpaddle-wheel subunits, are reported. 1crystallizes in the triclinic space group P
, witha = 6.8873(3) Å, b =11.7367(6) Å, c = 13.7899(7) Å, 
=107.076(4)
, 
= 93.545(4), 
=103.967(4), Z = 1. TheCu···Cudistance is 2.6009(4) Å, and the Cu···carboxylate Odistances are in the range 1.937(2)-1.962(2) Å. Theethanolat the apex forms an unsymmetrical bifurcated H bond to two carboxylateoxygens of another dinuclear unit withO···O distances 2.980(3) and 3.108(3) Å, therebyextending the structure along the a-axis. The magneticstructureconsists of isolated antiferromagnetically coupled dinuclear copperunits, with a -2J value of 242cm-1, inconcurrence with the EPR parameters, viz.,gx = 2.03(1),gy = 2.07(1),gz = 2.35(1),A
= 0.064(2)cm-1, D =0.316(15) cm-1, E =0.005(1) cm-1. The -2Jvalue is the smallest value measured for dinuclear coppercarboxylates with oxygen-donor ligands at the axial position and noelectron-withdrawing carboxylate R groups.2 crystallizes in the monoclinic space groupP21/c, with a =15.953(2) Å, b = 5.385(6) Å, c =28.322(10) Å, = 120.22(3), Z = 2. The compound containstetrakis(diphenylacetato)dicopper(II) units, forming apolymericstructure along the b-axis by axial coordination of a carboxylateoxygen to copper of a subsequent dinuclear unit,at 2.323(11) Å. The intradimer Cu···Cu distanceis 2.594(4) Å; the interdimer Cu···Cu distance is3.425(5) Å.The -2J value of 321 cm-1was interpreted as originated from isolated antiferromagneticallycoupled dinuclearcopper units. The EPR parameters aregx = 2.07(1),gy = 2.02(1),gz = 2.33(1), D =0.347(10) cm-1, E=0.0034(5) cm-1. The dinuclearsubunits are likely candidates for the catalytically active Cu speciesin copper(II)-catalyzed oxidation of carboxylic acids.
-1-phenylcyclopropane-1-carboxylato-O,O')bis(ethanol-O)dicopper(II)],1, andcatena-poly[[bis(-diphenylacetato-O:O')dicopper](3-diphenylacetato-1-O:2-O':1'-O')(3-diphenylacetato-1-O:2-O':2'-O')],2, two extended-chain copper(II) carboxylates withdinuclearpaddle-wheel subunits, are reported. 1crystallizes in the triclinic space group P, witha = 6.8873(3) Å, b =11.7367(6) Å, c = 13.7899(7) Å, =107.076(4), = 93.545(4), =103.967(4), Z = 1. TheCu···Cudistance is 2.6009(4) Å, and the Cu···carboxylate Odistances are in the range 1.937(2)-1.962(2) Å. Theethanolat the apex forms an unsymmetrical bifurcated H bond to two carboxylateoxygens of another dinuclear unit withO···O distances 2.980(3) and 3.108(3) Å, therebyextending the structure along the a-axis. The magneticstructureconsists of isolated antiferromagnetically coupled dinuclear copperunits, with a -2J value of 242cm-1, inconcurrence with the EPR parameters, viz.,gx = 2.03(1),gy = 2.07(1),gz = 2.35(1),A = 0.064(2)cm-1, D =0.316(15) cm-1, E =0.005(1) cm-1. The -2Jvalue is the smallest value measured for dinuclear coppercarboxylates with oxygen-donor ligands at the axial position and noelectron-withdrawing carboxylate R groups.2 crystallizes in the monoclinic space groupP21/c, with a =15.953(2) Å, b = 5.385(6) Å, c =28.322(10) Å, = 120.22(3), Z = 2. The compound containstetrakis(diphenylacetato)dicopper(II) units, forming apolymericstructure along the b-axis by axial coordination of a carboxylateoxygen to copper of a subsequent dinuclear unit,at 2.323(11) Å. The intradimer Cu···Cu distanceis 2.594(4) Å; the interdimer Cu···Cu distance is3.425(5) Å.The -2J value of 321 cm-1was interpreted as originated from isolated antiferromagneticallycoupled dinuclearcopper units. The EPR parameters aregx = 2.07(1),gy = 2.02(1),gz = 2.33(1), D =0.347(10) cm-1, E=0.0034(5) cm-1. The dinuclearsubunits are likely candidates for the catalytically active Cu speciesin copper(II)-catalyzed oxidation of carboxylic acids.