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Issue 43, 2016
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Synthesis of six-coordinate mono-, bis-, and tris(tetrazolato) complexes via [3 + 2] cycloadditions of nitriles to silicon-bound azido ligands

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Abstract

A convenient synthetic route to poly(tetrazolato) silicon complexes is described based on the four reactive centres of the N-rich, highly endothermic tetraazides of the type Si(N3)4(L2). Hypercoordinate azido(tetrazolato) silicon complexes Si(N3)2(N4C-R)2(L2), R = CH3, C6H5, 4-C6H4CH3 (4a, 5, 6, 7) and Si(N3)2(N4C-L)2 (9, L = 2-C5H4N), L2 = 2,2′-bipyridine, 1,10-phenanthroline, with SiN6 skeletons were synthesised via multiple [3 + 2] dipolar cycloaddition reactions starting from Si(N3)4(L2) and a nitrile. The isolated new complexes were characterised by standard analytical methods, single crystal X-ray diffraction and differential scanning calorimetry (4a,b). Tetrazolato ligand linkage isomerism was observed for complex 4a. The crystallographically characterised methyl tetrazolato complexes and plausible configurational and linkage isomers were evaluated by DFT calculations at the B3LYP/6-311G(d,p) level.

Graphical abstract: Synthesis of six-coordinate mono-, bis-, and tris(tetrazolato) complexes via [3 + 2] cycloadditions of nitriles to silicon-bound azido ligands

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Publication details

The article was received on 20 Jul 2016, accepted on 26 Sep 2016 and first published on 13 Oct 2016


Article type: Paper
DOI: 10.1039/C6DT02867E
Citation: Dalton Trans., 2016,45, 17141-17152
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    Synthesis of six-coordinate mono-, bis-, and tris(tetrazolato) complexes via [3 + 2] cycloadditions of nitriles to silicon-bound azido ligands

    P. Portius and M. Davis, Dalton Trans., 2016, 45, 17141
    DOI: 10.1039/C6DT02867E

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