9,10-Anthracene dicarboxylate bridged complexes with M2 quadruply bonded dimetal units: [[M2(O2CtBu)3]2(mu-9,10-An(CO2)2)], where M = Mo or W

Dalton Transactions : an International Journal of Inorganic Chemistry
Matthew J ByrnesJeffrey M Zaleski

Abstract

From the reactions between [M2(O2CtBu)4] and 9,10-anthracenedicarboxylic acid in toluene, the dicarboxylate bridged complexes [[M2(O2CtBu)3]2(mu-9,10An(CO2)2)], have been obtained as microcrystalline yellow (M = Mo) and red (M = W) powders. The powders are soluble in THF forming intense red (M = Mo) and green (M = W) solutions. The electronic absorption spectra in 2-MeTHF have been recorded as a function of temperature (2-298 K) and show a small bathochromic shift on cooling. The electronic structures have been investigated by molecular orbital calculations employing density functional theory on the model compounds [(HCO2)3M2]2(mu-9,10-An(CO2)2) where the M4 unit is constrained to lie in a plane. These reveal a minimum energy, gas-phase structure wherein the plane of the anthracene is twisted by ca. 54 degrees with respect to its 9,10-carboxylate units for both Mo and W. The results of these calculations are correlated with the electronic absorption spectral data and the electrochemical measurements (CV and DPV) of the first and second oxidation waves. The EPR spectra of the radical cations formed by single-electron oxidation with [Cp2Fe](+)[PF6]- in a THF-CH2Cl2 solvent mixture show that the complexes are valence trapped at am...Continue Reading

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Aug 10, 2000·Acta Crystallographica. Section C, Crystal Structure Communications·S JonesW Clegg
Oct 17, 2001·Accounts of Chemical Research·F A CottonC A Murillo
Sep 21, 2002·Chemical Communications : Chem Comm·B E BurstenP J Wilson
Oct 3, 2002·Chemical Communications : Chem Comm·Matthew J Byrnes, Malcolm H Chisholm

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Citations

Mar 13, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Douglas J BrownJudith C Gallucci
Jul 23, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Malcolm H Chisholm, Namrata Singh
Dec 13, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Malcolm H Chisholm, Nathan J Patmore
Jan 18, 2006·Inorganic Chemistry·F Albert CottonDino Villagrán
Dec 8, 2005·Journal of the American Chemical Society·Matthew J ByrnesClaudia Turro

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