MNE Nitrido Bridges with Transition Metal Nitrogen Multiple Bonds and E = Phosphorus, Sulfur, and Chlorine

Abstract

AbstractA compilation is given on new syntheses, properties, and structures of complexes with M≡N—E ↔ M=N=E nitrido bridges with transition metal nitrogen multiple bonds and participation of the main group elements E of phosporus, sulfur, and chlorine.1. MNP: This atomic sequence is realized in phosphoraneiminato complexes with transition metals in high oxidation states and termal bond of the (NPR3—) ligand. A series of new complexes of this type is reported with M = zirconium, hafnium, molybdenum, tungsten, and rhenium, among these the homoleptic species [Hf(NPPh3)4] and [M(NPPh3)4]2+ with M = Mo and W. Therefrom the isolobal complexes [:N≡Mo(NPPh3)3], [:O≡W(NPPh3)3]+, [(O)2Mo(NPPh3)2], and [(O)3Re(NPPh3)] are derived.2. MNS: Adding to compounds with this atomic sequence, new complexes were developed on the basis of the functional ligand groups thionitrosyl (a), dinitridosulphate(II) (b), dinitridosulphate(IV) (c), and cyclothiazeno (d) (cyclo‐3, 5‐dithia‐2, 4, 6‐triazino):magnified image3. MNCl: Novel N‐chloroimido complexes of tungsten are described. [F4W≡N—Cl]4, which is tetrameric according to the IR spectrum, was obtained by direct fluorination from [Cl4W≡N—Cl]2 or, surprisingly, from W(N)Cl3. With acetonitrile the monomeric molecular complex [CH3CN→WF4(≡N—Cl)] is formed. In an unexpected pathway K[F5W≡N—Cl] was obtained from a redox reaction of W(N)Cl3 with trimethylstannyl fluoride in the presence of potassium fluoride. The ionic compound forms double layers with short Cl···F contacts.