Dicationic Methyl Complexes of the Rare-Earth Elements

Abstract

The reactions of Ln(AlMe4)3 (Ln=Ho, Tm) with the crown ether [12]crown-4 yield dicationic methyl rare-earth metal complexes [LnMe([12]crown-4)2][AlMe4]2 (Ln=Ho (1), Tm (2)). The reaction of La(AlMe4)3 with [18]crown-6 in thf affords [LaMe([18]crown-6)(thf)2][AlMe4]2 (3). The compounds have been characterized by X-ray diffraction, 1 and 3 additionally by elemental analyses as well as by 1H and 27Al, and 3 also by 13C NMR spectroscopy

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2014

“…AlR 3 or AlH( i Bu) 2 R=Et or i Bu The closely related yttrium complex containing a chiral silicon-linked tridentate amido-indenyl ligand shown in Scheme 83 has also been found to efficiently catalyze the intramolecular hydroamination of non-activated olefins with up to 97% ee. [67] M a n u s c r i p t 99 Binaphthylamido alkyl yttrium complexes have been proven to efficiently promote the anti-Markovnikov addition between various styrene derivatives and secondary amines.…”

Rare Earth Starting Materials and Methodologies for Synthetic Chemistry

“…675 These starting materials can also be used to generate heteroleptic alkyl complexes with bidentate nitrogen donors, such as amidinates (257), 675 691 This synthetic approach has since been optimized by generating the amide precursors in situ from RECl 3 (THF) x and Li(NMe 2 ), and the methodology has been extended to most of the REs. 518,692,693 The overall reaction can be viewed as an amide-methyl metathesis generating Me 2 NAlMe 2 and putative methyl complex "RE(Me) 3 ", with the latter converted into 266-RE upon adduct formation with ). Organoaluminates obtained with these methods can cocrystallize with Al 2 Me 6 , which can be removed upon recrystallization.…”

Coordination Chemistry and Spectroscopic Properties of Eu(II), Sm(II), and Yb(II) with 12-Crown-4

“…Continuing with 12-crown-4 (12c4), a much smaller crown molecule than previously studied with Sm 2+ , is a natural extension of developing a thorough understanding of Ln 2+ /crown ether complexes. While numerous detailed structural studies of Ln 3+ /12c4 complexes have been performed, Ln­(12c4)­(NO 3 ) 3 , − [Ln­(12c4)­(OH 2 ) 5 ]­[Cl] 3 ·2H 2 O, , [Ln­(12c4)­(OH 2 ) 2 Cl 2 ]­Cl, [Ln­(12c4) 2 CH 3 ]­[Al­(CH 3 ) 4 ], , [Er­(12c4) 2 (CH 3 CN)]­[SbCl 6 ] 3 , [Dy­(12c4) 2 (CH 3 CN)]­[ClO 4 ] 3 , and others, only one Eu 2+ crystal structure has been measured with 12c4 . [Eu­(12c4)­(OH 2 ) 3 Cl]Cl was obtained by electrochemical reduction and exhibits 5d–4f photoluminescence with an emission of 410 nm at 77 K, blue-shifted from its room temperature emission of 429 nm .…”