[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)Cl-2(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) Angstrom. 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)Cl-2(Me2PhP)(3)] which is the first structurally characterized transition metal complex containing a nitrido bridge to unsubstituted borane.