Synthesis of Homo‐ and Heteroleptic Al, Ga and Zn Complexes Containing (Per)fluorinated β‐Diketiminate Ligands

Abstract

Alkane elimination reactions of equimolar amounts of 17Fnac2H (17Fnac2H = FC[C(CF3)NC6F5]2H) with ZnEt2 and AlMe3 as well as 16Fnac2H (16Fnac2H = HC[C(CF3)NC6F5]2H) with GaMe3 yielded the corresponding heteroleptic complexes of 17Fnac2ZnEt (1), 17Fnac2AlMe2 (2), and 16Fnac2GaMe2 (3), whereas reactions of two equivalents of 16Fnac2H and 17Fnac2H with either ZnEt2 or Cp*2Zn gave homoleptic ZnII complexes (16Fnac2)2Zn (4) and (17Fnac2)2Zn (5), respectively. 1–5 were characterized by IR and NMR spectroscopy (1H, 13C, 19F), elemental analysis and single‐crystal X‐ray diffraction.

Synthesis, Reactivity, and Lewis Acidity of Cationic Zinc Complexes

“…The C 3 N 2 Zn six-membered ring is almost planar (deviation from planarity for the zinc atom: 0.1750(25) Å), while the ipso carbon atom deviates from the ligand plane by 0.6275(50) Å (Table ). Due to the smaller σ donor ability of the fluorinated β-diketiminate ligand, an elongation of the Zn–N bond lengths and a shrinking of the N–Zn–N bond angles is observed for 16 Fnac 2 ZnC 6 F 5 in comparison to Dipp Nac 2 ZnC 6 F 5 , a feature that has been observed for all complexes synthesized in previous studies , containing these fluorinated β-diketiminate complexes.…”

“…A comparison of these complexes with analogous Cu­(I) complexes with classical (nonfluorinated) β-diketiminate substituents proved the reduced electron-donating properties of the fluorinated substituents. In addition, 16 Fnac 2 - and 17 Fnac 2 -substituted Zn, Al, and Ga complexes were synthesized and structurally characterized. − We now became interested in the capability of such weakly electron donating β-diketiminate ligands for the stabilization of cationic zinc complexes as well as their effect on the reactivity of the resulting cationic zinc complexes in comparison to known β-diketiminate-substituted zinc cations.…”

Fluorinated β‐Ketoiminate Zinc Complexes: Synthesis, Structure and Catalytic Activity in Ring Opening Polymerization of Lactide

“…Complex 3 also formed in an analogous reaction of complex 2 with benzyl alcohol (BnOH) under identical reaction conditions as was proven by 1 H and 19 F NMR spectroscopy (Figure S16 and S17). A similar reaction was previously observed in the reaction of a β ‐diketiminate zinc complex 16 Fnac 2 ZnEt with ArOH (Ar=2,6‐Me 2 ‐C 6 H 3 ) [14] …”

“…A similar reaction was previously observed in the reaction of a β-diketiminate zinc complex 16 Fnac 2 ZnEt with ArOH (Ar = 2,6-Me 2 -C 6 H 3 ). [14] Complexes 1-3 were characterized by heteronuclear NMR ( 1 H, 13 C, 19 F) and IR spectroscopy and their purity demonstrated by elemental analysis. The 1 H NMR spectra show the expected resonances of the C γ -H (1: 5.96 ppm, 2: 5.97 ppm, 3: 5.88 ppm) and the zinc methyl (δ À 0.72 1) and ethyl groups (δ 0.96, 0.22 2), respectively.…”

Metal Complexes of Donor‐functionalized Fluorinatedβ‐Ketoiminates – Synthesis, Structure, and CVD Application

“…Our interest in complexes containing β ‐diketiminate and β ‐ketoiminate substituents including donor‐functionalized ligands prompted our interest toward perfluorinated β ‐diketiminate ligands . We now extend these studies on partly fluorinated donor‐functionalized β ‐ketoiminate ligands and report on the synthesis and structures of six alkali metal complexes and one platinum complex, which was shown to be a suitable CVD precursor for the deposition of crystalline Pt films.…”