Abstract
[Tc(NBCl2Ph)Cl2(Me2PhP)3] and [Tc(NBH3)Cl2(Me2PhP)3] – the First Technetium Complexes with Nitrido Bridges between Technetium and Boron [TcNCl2(Me2PhP)3] reacts with BCl2Ph or BH3 · THF at low temperatures under formation of complexes containing a nitrido bridge between technetium and boron. The compounds are instable and decompose at room temperature under cleavage of the N–B bonds. The pale-purple [Tc(NBCl2Ph)Cl2(Me2PhP)3] crystallizes in the orthorhombic space group Fdd2. The Tc≡N bond is only slightly lengthened by the formation of the N–B bond of 1.564(4) A. However, a considerable lengthening of the Tc–Cl bond in trans position to the nitrido ligand is observed which can be attributed to an decreasing of the structural trans influence of the nitrido moiety. A similar structural feature can be found in [Tc(NBH3)Cl2(Me2PhP)3] which is the first structurally characterized transition metal complex containing a nitrido bridge to unsubstituted borane.
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