Novel, generally highly oxygen sensitive („hemi”︁) ClCrN(SiMe3)2(L)n, I, and Cr[N(SiMe3)2]2LL′, II, were prepared with L, L′ = (a) aliphatic and cyclic ethers (including polyfunctional ligands) (b) alkyl cyanides, (c) aromatic tertiary amines or (d) mixtures of a and c. The products are characterized by elemental analysis and chemical reactions. Representative reflectance spectra are presented.
Chemical and physical properties are strongly dependent on the nature of L, L′ and oxygen sensitivity, thermal stability, solubility and reactivity of the CrN linkage (in reactions with surface
) could be regulated by varying the coordinated ligands. Empirical reactivity series for various LL′ combinations and ligand lability interrelationships were established. Behavior of some complexes in Cr(II) alkoxide synthesis, ring opening polymerizations, and in pyrolysis reactions is discussed.