Lutetium Alkyls Supported by a Dearomatized and Functionalized Terpyridine Ligand: Preparation of Fluorinated Anilide Complexes

Abstract

Lutetium alkyl complexes supported by a monoanionic, tridentate ligand system formed by the dearomatization and functionalization of a 2,2′:6′,2′′-terpyridine have been reacted with 2,4,6-triphenylaniline or the fluorinated anilines 4-F-C6H4NH2 and C6F5NH2 to give both terminal mono(amide) and bis(amide) lutetium(III) complexes, which have been fully characterized. Both [ t Bu3(2′-Me3SiCH2)tpy]Lu[NH(2,4,6-Ph3-C6H2)]2 (3) and [ t Bu3(2′-Me3SiCH2)tpy](C5Me5)Lu(NHC6F5) (7) have been structurally characterized. The fluorinated anilide complexes [ t Bu3(2′-Me3SiCH2)tpy](C5Me5)Lu(NHArF) (ArF = 4-F-C6H4 (6), C6F5 (7)) provide rare examples of lutetium organofluorine complexes, with 7 featuring an intramolecular F···H−C interaction that is present in both solid state and solution.

Ruthenium Porphyrins with Axial π‐Conjugated Arylamide and Arylimide Ligands

“…Such distortion does not significantly alter the RuN(arylamide) distances in the complex. In the crystal structure of non‐porphyrin cis ‐bis(arylamide) complex [Lu( t Bu 3 {2′‐Me 3 SiCH 2 }tpy)(NH{ Ar  Ar ‐3,5‐Ph}) 2 ] (tpy=2,2′:6′,2′′‐terpyridine; Ar  Ar ‐3,5‐Ph=3,5‐diphenyl‐biphenyl‐4‐yl),4b the two phenyl rings of the biphenyl moiety of Ar  Ar ‐3,5‐Ph make larger dihedral angles of 35.3° and 43.7°.…”

Rare Earth Pincer Complexes: Synthesis, Reaction Chemistry, and Catalysis

“…The potential for this monoanionic tridentate NNN 0 ligand system to support multiply bonded rare earth species was examined a few years later when the alkyl amido and bis(amido) derivatives of complex 55 were prepared by alkane elimination reactions with different anilines. Unfortunately, thermolysis of the amido complexes did not result in the formation of the corresponding lutetium imido species, regardless of the nature of the anilide ligand [71].…”

Scandium, yttrium, the lanthanides

“…The bipy ligand is displaced by Ph 40 A dearomatized and functionalized terpyridine has similarly been used to support lutetium alkyls which are synthons for mono(amide) and bis(amide) complexes. 41 Simple alkyls like [Ln(CH 2 SiMe 3 ) 3 (thf) 2 ] continue to be used as suitable starting materials for the syntheses of other organometallics. 42 Ln(AlMe 4 ) 3 (Ln e.g.…”