Preparation of the hydrocarbon-soluble trifluoro complex LTiF3 with a β-diketiminato ligand

On the non-innocence of “Nacnacs”: ligand-based reactivity in β-diketiminate supported coordination compounds

“…83 Treatment of (HBDI*) with AgPF 6 in the presence of trimethylamine under anaerobic conditions in the absence of light results in the oneelectron oxidation of the ligand ultimately giving the dimeric enamine product and Ag(0) (Scheme 17top). 87 A similar process was observed with europium which can easily be reduced to the Eu(II) oxidation state possessing a stable half-filled f-shell 4f 7 electron configuration. Interestingly, BDI oxidative coupling is avoided when the ligand carbon framework does not carry alkyl substituents, allowing isolation of dinuclear Ag(I) complex [Ag 2 (BDI Dipp,H ) 2 ] (Scheme 17bottom).…”

“…10% yield from the salt metathesis reaction between KBDI and TiF 4 for the same reason. 87 A similar process was observed with europium which can easily be reduced to the Eu(II) oxidation state possessing a stable half-filled f-shell 4f 7 electron configuration. For instance, while the salt metathesis reaction between EuCl 3 and Na(BDI o-Tol,Me ) affords the expected Eu(III) complex Eu(BDI o-Tol,Me ) 3 , the same reaction conducted with the more sterically-hindered β-diketiminato Na(BDI Ar,Me ) anions (Ar = Dipp, Mes, Xy) yield the Eu(II) (BDI Ar,Me ) 2 Eu(THF) species together with the corresponding C-C coupled diamine products (Scheme 18 and Fig.…”

Titanium‐Catalyzed Vinylic and Allylic CF Bond Activation—Scope, Limitations and Mechanistic Insight

“…Acetonitrile, toluene, and pentane were dried over activated alumina using an MBraun solvent system model MB SPS‐800. [Cp 2 TiF 2 ] ( 1 a ),36 [Cp 2 TiH] ( 3 a ),22 [(Me 3 SiC 5 H 4 ) 2 TiCl 2 ],37 Me 3 SnF,10r [(Me 2 SiC 5 H 4 ) 2 TiCl 2 ],38 [(C 6 F 5 C 5 H 4 ) 2 TiCl 2 ],39 [(Me 3 SiC 5 H 4 )CpTiCl 2 ],40 [(Dipp 2 Nacnac)TiF 3 ] ( 1 i ),41 hexafluorocyclobutene ( 17 ),42 (Trifluoroethenyl)benzene ( 22 ),43 (trifluoroethenyl)ferrocene ( 25 ),20 [Cp 2 Ti(μ‐SiH 2 Ph)(μ‐H)TiCp 2 ] ( 31 b )23a tetrafluoroallene ( 29 ),35 and [Cp(CO) 3 CrH]44 were synthesized by literature procedures. [Cp 2 TiF] ( 32 ) was synthesized by a modified literature procedure45 using zinc instead of aluminum powder.…”