Phosphinohydrazines and phosphinohydrazides M(–N(R)–N(R)–PPh2)n of some transition and main group metals: synthesis and characterizationRearrangement of Ph2P–NR–NR– ligands into aminoiminophosphorane, RNPPh2–NR–, and related chemistry
| Autor: | Gleb A. Abakumov, Vyacheslav V. Sushev, Natalia P. Makarenko, Yurii A. Kursky, Tatiana G. Mushtina, Arnold L. Rheingold, Alexander N. Kornev, Georgy K. Fukin, Yana V. Fedotova, Lev N. Zakharov |
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| Rok vydání: | 2004 |
| Předmět: |
Diphenylphosphine
Chemistry Ligand Organic Chemistry Inorganic chemistry Biochemistry Medicinal chemistry Inorganic Chemistry Metal chemistry.chemical_compound Metal halides Main group element Transition metal Oxidation state visual_art Materials Chemistry visual_art.visual_art_medium Physical and Theoretical Chemistry Methylene |
| Zdroj: | Journal of Organometallic Chemistry. 689:3060-3074 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/s0022-328x(04)00470-x |
| Popis: | The reactions of phosphinohydrazines ArNH–N(Ar)–PPh2 {Ar = Ph (2a), p-But–C6H4– (2b)} with metal silylamides M[N(SiMe3)2]n, {M = Fe(II), Fe(III), Co(II), Ni(I), Cu(I)} or the reactions of lithium salts ArN(Li)–N(Ar)–PPh2 with metal halides (GeCl2, ZnCl2, FeBr2, CoCl2, NiBr2, CrCl3, MnCl2) are strongly dependent on nature of a metal and its ligand environment.Early transition metals or non-transition metals form stable phosphinohydrazides M[N(Ar)N(Ar)PPh2]n {M = Li, Zn, Ge(II), Mn(II), Cr(III), Fe(II)}.Starting ligand 2a and germylene Ge(NPhNPhPPh2)2 (7) were characterized by X-ray analysis.Germanium is coordinated additionally with a phosphorus atom of one of the diphenylphosphine groups.The distance Ge⋯P was found to be 2.563(1) A.This coordination leads to an appreciable increase in a pyramidal geometry of nitrogen atoms relatively to a non-coordinated fragment.Late transition metals (Co, Ni, Cu) and metals with enhanced oxidation state (Fe3+) cause transformation of a phosphinohydrazide ligand.For Co(II), Ni(II), Fe(III) this leads quantitatively to aminoiminophosphoranates M(NAr–PPh2 NAr)n.Complex Co[N(C6H4But)–PPh2 N–C6H4But]2 (11) was characterized by X-ray analysis.Nickel(I) silylamide, (Ph3P)2NiN(SiMe3)2, being reacted with 2a yields azobenzene complex, (Ph3P)2Ni(PhN NPh), while copper(I) silylamide originally forms (PhNH–NPh–PPh2)2CuN(SiMe3)2 (18).Heating of the latter in toluene solution yields insoluble copper(I) diphenylphosphide, azobenzene, 2a and hexamethyldisilazane.The reaction of hydrazobenzene with Ph2PCl (1:1) in methylene chloride for three days gives aminoiminophosphorane dihydrochloride[PhNH–PPh2 NPh] · 2HCl (3) in quantitative yield. |
| Databáze: | OpenAIRE |
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