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• W2023487269 endingPage "4240" @default.
• W2023487269 startingPage "4226" @default.
• W2023487269 abstract "Organometallic derivatives of scandium and yttrium supported by a bulky salicylaldiminato ligand were prepared from the tris(alkyl) precursors [M(CH2SiMe2R)3(THF)2] (M = Sc, 1-ScR; M = Y, 1-YR; R = CH3, Ph) via alkane elimination. The new precursors 1-MPh are convenient alternatives to the 1-MMe derivatives, due to their higher thermal stability and crystallinity; 1-ScPh has been characterized crystallographically. Reaction of these compounds with 1 equiv of protio ligand gives isolable mono(ligand) bis(alkyl) derivatives only for 1-Y; for other derivatives 1-Sc, mixtures were obtained. The products of the former reaction retain either two (2-YPh) or one (3-YPh) THF ligands; both of these compounds have been characterized crystallographically. In solution, both exhibit fluxional exchange between two geometric isomers which were characterized by variable-temperature NMR spectroscopy. Heating solutions of either compound leads to facile ligand redistribution. Reactions of tris(alkyls) 1 with 2 equiv of protio ligand gives the five-coordinate, THF-free bis(ligand) mono(alkyl) complexes 4-MR. These compounds are highly thermally stable, decomposing at temperatures above 140 °C via a pathway involving metalation of one of the N-aryl isopropyl methyl groups. The derivatives 4-ScMe and 4-YPh have been structurally characterized, as well as the product of thermolysis of 4-ScMe, the nonorganometallic four-coordinate complex 5-Sc. Both 4-ScMe and 4-YPh react slowly but cleanly with H2. The former yields a product, 7-Sc, derived from transfer of the in situ formed scandium hydride to the aldimine carbon of one of the ligands. The yttrium product, however, is the D2-symmetric dimeric μ-hydride complex 6-Y, characterized by spectroscopic and crystallographic methods. A survey of 6-Y’s reactivity toward deuterated solvents, d2-6-Y, ethylene, (trimethylsilyl)acetylene, [HB(C6F5)2]2, benzophenone, pyridine, and THF suggests that it does not dissociate into a monomeric hydride but reacts as a dimer. Nonetheless, products from the reactions of (trimethylsilyl)acetylene, [HB(C6F5)2]2, benzophenone, pyridine, and THF were isolated and characterized spectroscopically and, in the case of the product from the benzophenone reaction, crystallographically. Finally, reactions of mono(alkyls) 4-ScMe and 4-YPh with a further 1 equiv of protio ligand gave nonorganometallic tris(ligand) coordination complexes, both of which were structurally and spectroscopically characterized. The scandium derivative 8-Sc contained an O-bound κ1-salicylaldiminato ligand, while for 8-Y, containing the larger Y nucleus, all three ligands were chelating in the normal κ2 bonding mode." @default.
• W2023487269 created "2016-06-24" @default.
• W2023487269 creator A5011826172 @default.
• W2023487269 creator A5039366959 @default.
• W2023487269 creator A5075232878 @default.
• W2023487269 creator A5089752411 @default.
• W2023487269 date "2002-08-27" @default.
• W2023487269 modified "2023-10-02" @default.
• W2023487269 title "Organometallic Complexes of Scandium and Yttrium Supported by a Bulky Salicylaldimine Ligand" @default.
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• W2023487269 doi "https://doi.org/10.1021/om020382c" @default.

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