Electronically-coupled tungsten-tungsten quadruple bonds: comparisons of electron delocalization in 3,6-dioxypyridazine and oxalate-bridged compounds

Journal of the American Chemical Society
Malcolm H ChisholmNathan J Patmore

Abstract

The preparation of the 3,6-dioxypyridazine-bridged tungsten complex, [W(2)(O(2)C(t)Bu)(3)](2)(mu-H(2)C(4)N(2)O(2)), I, is described, along with its single-electron oxidized cation, I(+), formed in the reaction between I and Ag(+)PF(6)(-). Compound I has been structurally characterized as a PPh(3) adduct, and I(+)PF(6)(-) as a THF solvate, by single-crystal X-ray studies. The geometric parameters of these compounds compare well with those calculated for the model compounds [W(2)(O(2)CH)(3)](2)(mu-H(2)C(4)N(2)O(2)) and [W(2)(O(2)CH)(3)](2)(micro-H(2)C(4)N(2)O(2))(+) by density functional theory employing the Gaussian 98 and 03 suite of programs. The calculations indicate that the two W(2) centers are strongly coupled by M(2) delta-to-bridge pi-bonding, and further coupled by direct M(2)...M(2) bonding. Compound I is purple and shows an intense absorption in the visible region due to a metal-to-bridge charge transfer and, with excitation within this absorption, compound I exhibits pronounced resonance Raman bands associated with symmetric vibrations of the bridge and the M(4) unit. The cyclic voltammogram of I in THF, the EPR spectrum of I(+)PF(6) in 2-MeTHF and the electronic absorption spectrum of I(+)PF(6)(-) in THF are consist...Continue Reading

References

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Citations

Oct 8, 2005·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Malcolm H Chisholm, Nathan J Patmore
Mar 12, 1992·Biochimica Et Biophysica Acta·M Chu-PingG N DeMartino
Jan 17, 1993·Biochimica Et Biophysica Acta·L L HuangA Taylor
Dec 14, 1995·Biochimica Et Biophysica Acta·T AkaishiH Sawada
Sep 1, 1994·Trends in Biochemical Sciences·J M Peters
Jan 23, 2013·Journal of the American Chemical Society·Luke A WilkinsonNathan J Patmore
Feb 15, 2007·Proceedings of the National Academy of Sciences of the United States of America·Malcolm H Chisholm
Sep 12, 2007·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Malcolm H Chisholm
Feb 9, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Moumita MajumdarJitendra K Bera
Aug 15, 2014·Journal of the American Chemical Society·Zhi CaoTong Ren
Jun 28, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Malcolm H Chisholm, Nathan J Patmore
Dec 13, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Malcolm H Chisholm, Nathan J Patmore
Dec 20, 2007·Chemical Communications : Chem Comm·F Albert CottonJoseph H Reibenspies
May 7, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Malcolm H ChisholmNathan J Patmore
Aug 21, 2007·Inorganic Chemistry·F Albert CottonCarlos A Murillo
May 31, 2014·Journal of the American Chemical Society·Mario CarrascoErnesto Carmona
Dec 8, 2005·Journal of the American Chemical Society·Matthew J ByrnesClaudia Turro
Oct 27, 2005·Journal of the American Chemical Society·Mikhail V BarybinDavid J Zipse

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