Transition metal pnictides

Among binary transition-metal pnictides, only the first-row transition-metal phosphides have been analysed by XPS extensively, whereas arsenides and antimonides have been barely studied [51-61]. Table 2 reveals some general trends in the P 2p3/2 BEs for various first-row transition-metal monophosphides, as well as some metaland phosphorus-rich members forming for a given transition metal. Deviations of as much as a few tenths of an electron volt are seen in the BEs for some compounds measured multiple times by different investigators (e.g., MnP), but these... 

Transition Metal Pnictides and Compounds with Group IV Elements. 

Briick E, Trung NT, Ou ZQ, Buschow KHJ. Enhanced magnetocaloric effects and tunable thermal hysteresis in transition metal pnictides. Scripta Materialia. 2012 67 590-593. DOI 10.1016/j.scriptamat.2012.04.037. 

Kim YK, Cho YW (2005) Synthesis of transition metal pnictide nanocrystalline powders by mechanochemical reaction. J Alloys Compd 393 211-218... 

Carmalt CJ, Morrison DE, Parkin IP (2000) Liquid-mediated metathetieal synthesis of binary and ternary transition-metal pnictides. Polyhedron 19 829-833... 

F. Hulliger, Crystal chemistry of the chalcogenides and pnictides of the transition metals. Struct. Bonding 4 (1968) 82. 

A large variety of ligands form bonds with transition metals via one or more pnictide atoms. These range from simple ER3 (E = P, As, Sb, Bi R = alkyl, aryl, alkoxy, aryloxy, halogen and their combinations/permutations) molecules to ligands of elaborate architecture such as the macrocycles described in Section 14.2.1.7. 

Pnictide-transition metal bonds are essentially covalent coordinate, in which the pnictide provides the electrons. However, this simple picture does not account for all the structural data now available. The consensus view is that three factors are involved in the ligand contribution to the M—E bond (a) a bonding (Section 14.4.2), (b) n bonding (Section 14.4.3), and (c) steric factors (Section 14.3). The effect of the metal will not be discussed here, except insofar as individual complexes are used as examples. 

---