Preparation, characterization, and theoretical analysis of group 14 element(I) dimers: a case study of magnesium(I) compounds as reducing agents in inorganic synthesis

Cameron Jones, Simon Bonyhady, Nicole Holzmann, Gernot Frenking, Andreas Stasch

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A synthetic route to the new amidine (DipNH)(DipN)-C(C(6)H(4)Bu(t)-4) (ButisoH; Dip = C(6)H(3)Pr(2)(i)-2,6) has been developed. Its deprotonation with either LiBu(n) or KN(SiMe(3))(2) yields the amidinate complexes [M(Butiso)] (M = Li or K). Their reactions with group 14 element halides/pseudohalides afford the heteroleptic group 14 complexes [(Butiso)SiCl(3)], [(Butiso)ECI] (E = Ge or Sn), and [ (Butiso)-Pb(mu-O(3)SCF(3))(THF) (infinity)], all of which have been crystallographically characterized. In addition, the synthesis and spectroscopic characterization of the homoleptic complex [Pb(Butiso)(2)] is reported. Reductions of the heteroleptic complexes with a soluble magnesium(I) dimer, [ ((Mes)Nacnac)Mg (2)] ((Mes)Nacnac = [(MesNCMe)(2)CH](-); Mes = mesityl), have given moderate-to-high yields of the group 14 element(I) dimers [ (Butiso)E (2)] (E = Si, Ge, or Sn), the X-ray crystallographic studies of which reveal trans-bent structures. The corresponding lead(I) complex could spectroscopic and theoretical analyses of [ (Butiso)E (2)] have allowed their properties to be compared. All complexes possess E-E single bonds and can be considered as intramolecularly base-stabilized examples of ditetrelynes, REER. Taken as a whole, this study highlights the synthetic utility of soluble and easy to prepare magnesium(I) dimers as valuable alternatives to the harsh, and often insoluble, alkali-metal reducing agents that are currently widely employed in the synthesis of low-oxidation-state organometallic/inorganic complexes.
Original languageEnglish
Pages (from-to)12315 - 12325
Number of pages11
JournalInorganic Chemistry
Issue number24
Publication statusPublished - 2011

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