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Issue 7, 1994
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Non-oxo chemistry of manganese in high oxidation states. Part 1. Mononuclear tert-butylimido compounds of manganese-(VII) and -(VI)

Abstract

The interaction of manganese(III) chloride in acetonitrile with NHR(SiMe3)(R = But or CMe2CH2Me) gave the manganese(VII) species Mn(NR)3Cl as thermally and air-stable green crystals. The chlorine atom in Mn(NBut)3Cl 1 has been substituted by Br, OC(O)R (R = Me or CF3). OC6X5(X = F or Cl), OCH(CF3)2′ SC6F5′ C6F5 or NHBut by use of SiMe3Br and the silver, thallium or lithium salts of other reagents. Interaction of compound 1 with Ag(O3SCF3) or AgPF6 and NH2But gave the salts of the cation [Mn(NBut)3(NH2But)]+, with Li(NHBut) under selected conditions gave the paramagnetic manganese(VI) analogues of the manganate(VI) anion, [LiL]2[Mn(NBut)4][L = 1,2-dimethoxyethane (dme) or N,N,N′,N′-tetramethylethylenediamine (tmen)], and with HCl gave Mn(NBut)2(NHBut)Cl2, the reaction being reversed by addition of pyridine. Unstable compounds, e.g Mn(NBut)3(C6F5) and Mn(NBut)3(NHBut), were characterised spectroscopically. The mechanism of the formation of 1 is discussed together with a mechanism accounting for the instability of compounds where the X-group has β-H atoms as in Mn(NBut)3[OCH(CF3)2]. β-Hydrogen transfer to a NBut group to give a manganese(V) dimer [Mn(NBut)2(NHBut)]2 occurs with the formation of ketones from alkoxides; for alkyls decomposition appears to involve homolysis of the Mn–C bond and a radical pathway. The crystal structures of the compounds Mn(NBut)3X, X = OC(O)Me, OC6F5, SC6F5, [Mn(NBut)3(NH2But)]Y, Y = CF3SO3 or PF6 and [Li(dme)]2[Mn(NBut)4] have been determined. In all the compounds the manganese atom has distorted tetrahedral geometry. In the first three the Mn–N(imido) bond lengths are 1.664(3)–1.673(9)Å and the Mn–N–C angles 139.9(2) to 144.6(3)°, indicating partial multiple-bond character. The Mn–X distances, 1.91(3), 1 896(2) and 2.289(1)Å respectively indicate single bonds. In the cationic compounds the Mn–N(imido) distances are 1.531 (8)–1.655(8)Å, with Mn–N–C angles of 1 35.8(6)–170.2(9)°, suggesting more uneven distribution of the Mn–N multiple bonding, although these structures were less precisely determined due to disorder. In the manganate(VI) anion the Mn–N(imido) lengths are longer, 1.746(3)–1.749(3)Å, as expected.

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Article type: Paper
DOI: 10.1039/DT9940001037
Citation: J. Chem. Soc., Dalton Trans., 1994,0, 1037-1049
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    Non-oxo chemistry of manganese in high oxidation states. Part 1. Mononuclear tert-butylimido compounds of manganese-(VII) and -(VI)

    A. A. Danopoulos, G. Wilkinson, T. K. N. Sweet and M. B. Hursthouse, J. Chem. Soc., Dalton Trans., 1994, 0, 1037
    DOI: 10.1039/DT9940001037

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