Ethylzinc‐ and Zinc–bis–fluoroalkoxides

Abstract

We describe synthesis routes from fluorinated ethylzinc alkoxides to ether adducts of fluorinated binary homoleptic zinc alkoxides with fluorinated residues such as ORF (OC(CF3)3), ORHF (OC(H)(CF3)2), ORHT (OC(CH3)(CF3)2), ORAF (perfluoroadamantoxy) and ORCY (OC(CF3)(CF2)5). Their structures depend on the nature of the fluorinated residue: perfluorinated alkoxides ORXF tend to give monomeric ether adducts (ether)2Zn(ORXF)2, while partially fluorinated residues ORYF lead to dimers of type (ether)(YFRO)Zn(μ‐ORYF)2Zn(ORYF)(ether). The monomeric (Et2O)2Zn(ORF)2 was tested for its possibility to form fluorine doped zinc oxide upon thermal decomposition in inert atmosphere. Indeed, upon thermal degradation, homogenously doped materials (EDX mapping) with fluoride contents of 5.5 to 6 weight‐% form (EDX, ion chromatography).

Metal Complexes of the Perfluorinated Trityl Alkoxide [(C6F5)3CO]−

“…Thus, the zinc atoms are located within a trigonal planar coordination environment and furthermore coordinated by two fluorine atoms with Zn⋅⋅⋅F distances of 2.5797(8) and 2.8724(7) Å. It has been described that the nuclearity of zinc alcoholates is determined by the steric demand and the electronic structure of the alcohol as well as the presence or absence of donor molecules [15–17] . A similar dimeric structure to [ZnEt(OC(C 6 F 5 ) 3 )] 2 has been reported for the perfluorinated tert ‐butyl alcoholate [ZnEt(OC(CF 3 ) 3 )] 2 by Krossing and coworkers [15] .…”

Ligand and metal-centred reactivity in 2,6-bis(imino)-1,4-dihydropyridinate Zn(ii) alkyls: the dual behaviour of an intriguing type of complex

“…After filtration, the 19 F NMR spectrum of the supernatant solution shows a number of signals, likely arising from oligomeric zinc fluoroalkoxides. 21 However, if equimolar amounts of the corresponding fluoroalcohol are used, new complexes were formed, whose signals are observed in the 1 H NMR spectra of the reaction mixtures, along with those of the corresponding R–H (toluene from 1-Bn or methane from 1-Me ). For each fluoroalcohol, the NMR spectrum of the main product is the same, independently of the starting material ( 1-Bn or 1-Me ).…”

Three Fluorinated Trityl Alcohols and their Lithium Salts – Synthesis, Molecular Structures, and Acidity

“…Interactions between organically bound fluorine atoms and metal ions across the periodic table have been the subject of intensive scientific interest, which was highlighted in two review articles by Plenio . For instance, metal salts with lithium, sodium, potassium, alkaline earth metals,[4b], vanadium, niobium, molybdenum, tungsten, iron, cobalt, copper, silver,[3a], zinc, tin, thallium,[11b] uranium or europium revealing various metal fluorine contacts are described for complexes derived from (CF 3 ) 3 COH. Furthermore, the combination of sterically demanding fluorinated alcohols with group 13 metals is a recurrent strategy for the design of extraordinarily strong Lewis acids as documented by Krossing's PhF · Al(OC(CF 3 ) 3 ) 3 and Al(O(C 6 F 10 (C 6 F 5 ))) 3 .…”