Lanthanide(III)/actinide(III) differentiation in coordination of azine molecules to tris(cyclopentadienyl) complexes of cerium and uranium

Dalton Transactions : an International Journal of Inorganic Chemistry
Thouraya MehdouiMichel Ephritikhine

Abstract

Reaction of azine molecules L with the trivalent metallocenes [M(C5H4R)3](M = Ce, U; R = But, SiMe3) in toluene gave the Lewis base adducts [M(C5H4R)3(L)](L = pyridine, 3-picoline, 3,5-lutidine, 3-chloropyridine, pyridazine, pyrimidine, pyrazine, 3,5-dimethylpyrazine and s-triazine), except in the cases of M = U and L = 3-chloropyridine, pyridazine, pyrazine and s-triazine where oxidation of U(III) was found to occur. In the pairs of analogous compounds of Ce(III) and U(III), i.e.[M(C5H4But)3(L)](L = pyridine, picoline) and [M(C5H4SiMe3)3(L)](L = pyridine, lutidine, pyrimidine and dimethylpyrazine), the M-N and average M-C distances are longer for M = Ce than for M = U; however, within a series of azine adducts of the same metallocene, no significant variation is noted in the M-N and average M-C distances. The equilibria between [M(C5H4R)3], L and [M(C5H4R)3(L)] were studied by 1H NMR spectroscopy. The stability constants of the uranium complexes, KUL, are greater than those of the cerium counterparts, KCeL. The values of KML are much greater for R = SiMe3 than for R = But and a linear correlation is found between the logarithms of KML and the hydrogen-bond basicity pKHB scale of the azines. Thermodynamic parameters indicate th...Continue Reading

Citations

Aug 27, 2013·Inorganic Chemistry·Charles de SahbBenjamin P Hay
Jun 2, 2005·Chemical Communications : Chem Comm·Thouraya MehdouiMichel Ephritikhine
Aug 2, 2014·Inorganic Chemistry·Dominik P HalterKarsten Meyer
Sep 29, 2011·Chemistry : a European Journal·Stefan G MinasianJohn Arnold
Sep 29, 2012·Chemistry : a European Journal·Benjamin OelkersRhett Kempe
May 24, 2006·Dalton Transactions : an International Journal of Inorganic Chemistry·Michel Ephritikhine
Mar 23, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Thouraya MehdouiMichel Ephritikhine
Jun 4, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Jean-Claude BerthetMichel Ephritikhine
Jul 27, 2010·Chemistry : a European Journal·Polly L ArnoldRobert P Tooze
Jan 7, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Zhi-Wei HuangWei-Qun Shi
Jul 26, 2019·Chemical Science·Justin N CrossNicola Lanata
Mar 31, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Wenshan RenMarc D Walter
Aug 30, 2018·Chemistry : a European Journal·Olaf Walter
Oct 22, 2020·Angewandte Chemie·Dieuwertje K ModderMarinella Mazzanti
Mar 19, 2008·Inorganic Chemistry·Mathieu RogerMichel Ephritikhine
Dec 23, 2009·Inorganic Chemistry·Karsten Krogh-JespersenJohn G Brennan
Aug 4, 2010·Inorganic Chemistry·Olivier BénaudMichel Ephritikhine
Jun 17, 2014·Inorganic Chemistry·Alexandre HervéMichel Ephritikhine
Feb 1, 2005·Inorganic Chemistry·Mathieu RogerMichel Ephritikhine

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