The first all-nitrogen coordinated bis(alkylamidinato)/bis(alkylimido) complexes of molybdenum and tungsten, [Mo(NtBu)(2){(iPrN)(2)CMe}(2)]and [W(NtBu)(2){(iPrN)(2)CMe}(2)], have been synthesized and fully characterized by H-1 and C-13 NMR spectroscopy, elemental analyses, high-resolution electron impact mass spectrometry, and Fourier transform infrared spectroscopy. Density functional theory calculations of the tungsten complex allow for geometry optimization and structural characterization by assignment of the NMR data, in particular a comparison of the experimental C-13 NMR signals with the calculated ones. Both compounds sublime without decomposition at 130 degrees C and 1 mTorr and show rapid decomposition above 250 degrees C, hence representing promising vapor-phase deposition routes for metal nitride based thin-film materials.