Borohydride, azide, and chloride anions as terminal ligands on Fe/Mo/S clusters. Synthesis, structure and characterization of [(Cl4-cat)(PPr3) MoFe3S4(X)2]2(Bu4N)4 and [(Cl4-cat)(PPr3)MoFe3S4 (PPr3)(X)]2(Bu4N)2 (X = N3-, BH4-, Cl-) double-fused cubanes. NMR reactivity studies of [(Cl4-cat)(PPr3) MoFe3S4(BH4)2]2(Bu4N)4

Inorganic Chemistry
Markos KoutmosDimitri Coucouvanis

Abstract

Our explorations of the reactivity of Fe/Mo/S clusters of some relevance to the FeMoco nitrogenase have led to new double-fused cubane clusters with the Mo2Fe6S8 core as derivatives of the known (Cl4-cat)2Mo2Fe6S8(PPr3)6 (I) fused double cubane. The new clusters have been obtained by substitution reactions of the PPr3 ligands with Cl-, BH4-, and N3-. By careful control of the conditions of these reactions, the clusters [(Cl4-cat)(PPr3)MoFe3S4(BH4)2]2(Bu4N)4 (II), [(Cl4-cat)(PPr3)MoFe3S4(PPr3)(BH4)]2(Bu4N)2 (III), [(Cl4-cat)(PPr3)MoFe3S4(N3)2]2(Bu4N)4 (IV), [(Cl4-cat)(PPr3)MoFe3S4(PPr3)(N3)]2(Bu4N)2 (V), and [(Cl4-cat)(PPr3)MoFe3S4Cl2]2(Et4N)4 (VI) have been obtained and structurally characterized. A study of their electrochemistry shows that the reduction potentials for the derivatives of I are shifted to more positive values than those of I, suggesting a stabilization of the reduced clusters by the anionic ligands BH4- and N3-. Using 1H NMR spectroscopy, we have explored the lability of the BH4- ligand in II in coordinating solvents and its hydridic character, which is apparent in its reactivity toward proton sources such as MeOH or PhOH.

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Citations

May 1, 2008·Journal of the American Chemical Society·Ying YuPatrick L Holland
May 22, 2010·Angewandte Chemie·Andreas K A Persson, Jan-E Bäckvall
Sep 17, 2010·Angewandte Chemie·Peter PortiusKlaus-Dieter Wehrstedt
Dec 24, 2018·Chemistry : a European Journal·Julian TeichmannMatthias Wagner
Jan 25, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Nikolay A PushkarevskyManfred Scheer
Jul 3, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Nicolas FrankRobert Langer
Nov 15, 2008·Journal of the American Chemical Society·Yasuhiro OhkiKazuyuki Tatsumi
Apr 30, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Lian XueXu-Dong Chen
Jan 16, 2015·Journal of the American Chemical Society·Abhishek BanerjeeMercouri G Kanatzidis
Jun 6, 2012·Journal of the American Chemical Society·Benjamin D YuhasMercouri G Kanatzidis

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