Main‐Group‐Metal and Transition‐Metal Complexes Containing Fluorinated β‐Diketiminate Ligands

Abstract

The synthesis of fluorinated -diketimine LH 1 (L = HC[C(CF 3 )NC 6 F 5 ] 2 ) and its reactions with main-group-metal and transition-metal complexes, yielding LAlMe 2 4, LZnEt 5, LCu(C 6 D 6 ) 6 and LCuCO 7, is reported. 1-7 were characterized [a]

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.…”

“…Karl Fischer titration of the dry solvents showed values of less than 2 ppm. 16 Fnac 2 ZnEt was prepared according to the literature procedure . [Ph 3 C]­[X] salts were prepared by the reactions of Na­[B­(C 6 F 5 ) 4 ], Li­[Al­{OC­(CF 3 ) 3 } 4 , AgSbF 6 , and NaBF 4 with Ph 3 CCl in CH 2 Cl 2 and were precipitated by addition of n -hexane and isolated by filtration.…”

“…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.…”

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

“…Our interest in complexes containing β-diketiminate [17] and β-ketoiminate substituents [18] including donor-functionalized ligands [19] prompted our interest toward perfluorinated β-diketiminate ligands. [20] 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.…”

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

“…The ketoimine ligands were prepared according to literature procedures. [18] 1 H, 13 C, and 19 F NMR spectra were measured at 297 K in CDCl 3 , CD 2 Cl 2 and toluene-d 8 using a Bruker Avance 300 spectrometer with a QNP probe head ( 1 H: 300 MHz, 13 C: 75 MHz, 19 F: 282 MHz), a Bruker Avance 400 ( 1 H: 400 MHz, 13 C: 100 MHz, 377 MHz) or a Bruker DRX 600 ( 1 H: 400 MHz, 13 C: 100 MHz, 19 F: 565 MHz) and referenced to the solvent shifts (CDCl 3 : 1 H = 7.26 ppm, 13 C = 77.16 ppm; CD 2 Cl 2 : 1 H = 5.32 ppm, 13 C = 53.84 ppm; toluene-d 8 : 1 H = 7.00 ppm, 13 C = 128.33 ppm). IR spectra were recorded in a glovebox under Ar atmosphere using an ALPHAÀ T FT-IR spectrometer equipped with a single reflection ATR sampling module.…”