ChemInform Abstract: Sulfur-Nitrogen-Bonded Metal Chelates. Part 16. Reactivities of Coordinated Nitriles in the Nickel(II) Complexes (Ni(S N N)(NCR))(ClO4) with Alcohols, Amines, and Different Nucleophiles. Synthesis, Characterization, and Stereochemistry of Imino-Ether, Amide, and Amidine Complexes.
Abstract
The nitrile complexes (I) are prepared from their neutral chloro analogues by chloride abstraction using AgClO4 and nitrile addition.
ChemInform Abstract
The nitrile complexes (I) are prepared from their neutral chloro analogues by chloride abstraction using AgClO4 and nitrile addition. The reactions of these complexes (I) with dry alcohols, wet alcohols, sec. aliphatic and heterocyclic amines, aliphatic prim. amines, water, PPh3, Ph2P(CH2)2PPh2, pyridine, NH3, and some anions (N3-, CN-, NCO-) are investigated. According to the conditions as shownby some examples, these reactions lead to the imino-ether complexes (II), to the amido complexes (III), or to the amidine complexes (VI). Water, PPh3, pyridine, and NH3 displace the nitrile ligand to give the adducts (VIII); Ph2P(CH2)2PPh2 react in the same way and yields the binuclear analogue. The reactions with the anions N3-, CN-, and NCO- generate the corresponding neutral substitution products. The 1H NMR spectra of the imino-ether and amidine complexes reveal the presence of two (E and Z) isomeric species, whose distribution at ambient temp. is determined.
