Zinc chalcogenolate complexes as precursors to ZnE and Mn/ZnE (E = S, Se) clusters

Inorganic Chemistry
Chhatra B KhadkaJohn F Corrigan

Abstract

The ternary clusters (tmeda)(6)Zn(14-x)Mn(x)S(13)Cl(2) (1a-d) and (tmeda)(6)Zn(14-x)Mn(x)Se(13)Cl(2) (2a-d), (tmeda = N,N,N',N'-tetramethylethylenediamine; x ≈ 2-8) and the binary clusters (tmeda)(6)Zn(14)E(13)Cl(2) (E = S, 3; Se, 4;) have been isolated by reacting (tmeda)Zn(ESiMe(3))(2) with Mn(II) and Zn(II) salts. Single crystal X-ray analysis of the complexes confirms the presence of the six "(tmeda)ZnE(2)" units as capping ligands that stabilize the clusters, and distorted tetrahedral geometry around the metal centers. Mn(II) is incorporated into the ZnE framework by substitution of Zn(II) ions in the cluster. The polynuclear complexes (tmeda)(6)Zn(12.3)Mn(1.7)S(13)Cl(2)1a, (tmeda)(6)Zn(12.0)Mn(2.0)Se(13)Cl(2)2a, and (tmeda)(6)Zn(8.4)Mn(5.6)Se(13)Cl(2)2d represent the first examples of "Mn/ZnE" clusters with structural characterization and indications of the local chemical environment of the Mn(II) ions. The incorporation of higher amounts of Mn into 1d and 2d has been confirmed by elemental analysis. Density functional theory (DFT) calculations indicate that replacement of Zn with Mn is perfectly feasible and at least partly allows for the identification of some sites preferred by the Mn(II) metals. These calculations, co...Continue Reading

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Citations

Dec 12, 2012·Analytical Chemistry·Amanda N ComeauLars Konermann
Feb 24, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Jessie L BrownAndrew J Gaunt
Aug 16, 2014·Chemical Communications : Chem Comm·Jens P Eussner, Stefanie Dehnen
Nov 22, 2014·Chemical Communications : Chem Comm·Bahareh Khalili Najafabadi, John F Corrigan
Oct 7, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Eliza LeusmannStefanie Dehnen
Jul 18, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Bahareh Khalili Najafabadi, John F Corrigan
Apr 18, 2015·Chemical Communications : Chem Comm·Mahmood Azizpoor FardJohn F Corrigan
Jan 3, 2019·Chemistry : a European Journal·Eike DornsiepenStefanie Dehnen
Nov 13, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Charlene A SmithRichard A Layfield
Nov 10, 2020·Small·Megalamane S BootharajuTaeghwan Hyeon

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