The semiquinone-ruthenium combination as a remarkably invariant feature in the redox and substitution series [Ru(Q)(n)(acac)(3-n)](m), n = 1-3; m = (-2), -1, 0, +1, (+2); Q = 4,6-Di-tert-butyl-N-phenyl-o-iminobenzoquinone

Inorganic Chemistry
Dipanwita DasGoutam Kumar Lahiri

Abstract

Three new compounds, [Ru(Q(*-))(acac)(2)] = 1, [Ru(Q(*-))(2)(acac)] = 2, and [Ru(Q(*-))(3)] = 3, were obtained and characterized as Ru(III) complexes with 4,6-di-tert-butyl-N-phenyl-o-iminobenzosemiquinone (Q(*-)) ligands. All three systems show multiple electron transfer behavior, which was analyzed using electron paramagnetic resonance (EPR) and UV-vis-near-infrared (NIR) spectroelectrochemistry. (1)H NMR spectroscopy and a crystal structure analysis suggest antiferromagnetically spin-spin coupled Ru(III) and Q(*-) in 1, similar to that in the related compound 4 with unsubstituted o-iminobenzosemiquinone. However, in contrast to 4(n) (Remenyi, C.; Kaupp, M. J. Am. Chem. Soc. 2005, 127, 11399), the system 1(m) exhibits unambiguously metal-centered electron transfer, producing ions [Ru(IV)(Q(*-))(acac)(2)](+) = 1(+) and [Ru(II)(Q(*-))(acac)(2)](-) = 1(-), both with EPR-evidenced ligand-based spin, as also supported by DFT calculations. Compared with the related redox system [Ru(Q)(bpy)(2)](k) (5(k)) (k = 0-3), the spectroelectrochemical similarity suggests corresponding electronic structures except for the 1(+)/5(3+) pair (Ru(IV)(Q(*-))(acac)(2)](+) (1(+)) versus [Ru(III)(Q(0))(bpy)(2)](3+) (5(3+))). Compound 2, a three-spin sy...Continue Reading

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Citations

Apr 27, 2011·Inorganic Chemistry·Tanaya KunduGoutam Kumar Lahiri
Jul 13, 2011·Inorganic Chemistry·Wolfgang Kaim
Jun 6, 2012·Inorganic Chemistry·Manas Kumar BiswasPrasanta Ghosh
Jun 22, 2013·Inorganic Chemistry·Suman KunduPrasanta Ghosh
Aug 6, 2015·Inorganic Chemistry·Abhishek MandalGoutam Kumar Lahiri
Nov 12, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Travis Marshall-Roth, Seth N Brown
Oct 23, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Alexander N Erickson, Seth N Brown
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Goutam Kumar Lahiri, Wolfgang Kaim
Jul 22, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Dipanwita DasGoutam Kumar Lahiri
Jan 11, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Hemlata AgarwalaGoutam Kumar Lahiri
May 28, 2019·Chemistry : a European Journal·Farheen Fatima KhanGoutam Kumar Lahiri
Dec 7, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Abhishek MandalGoutam Kumar Lahiri
May 6, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Jacqueline Gianino, Seth N Brown
Sep 25, 2012·Chemistry : a European Journal·Amit DasGoutam Kumar Lahiri
Aug 3, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Ankita DasGoutam Kumar Lahiri
Aug 10, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Dipanwita DasGoutam Kumar Lahiri
Jan 29, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Suman KunduPrasanta Ghosh
Jan 23, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Hemlata AgarwalaGoutam Kumar Lahiri
Jun 20, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Atanu Kumar DasWolfgang Kaim
Nov 3, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Anannya SahaRabindranath Mukherjee
Aug 20, 2014·Inorganic Chemistry·Prasenjit MondalGoutam Kumar Lahiri
Nov 23, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Sudip Kumar Bera, Goutam Kumar Lahiri

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