Issue 13, 2024

Tuning rare-earth hydride reactivity with a reductive diazabutadienyl ligand beyond insertion

Abstract

A new strategy for tuning rare-earth hydride reactivity has been developed using a reductive ligand. The reaction of diazabutadienyl-supported rare-earth hydride [(DAD)Y·THF]2(μ-H)2 (DAD = N,N′-di(2,6-diisopropylphenyl)-1,4-diazabutadienyl dianion), (1) with two equiv. of Ph2CO gave a reduced Ph2CO-coupled product (DAD′Y)2(μ-H)2(μ-η21-Ph2C(O)C(O)Ph2)(THF) (DAD′ = N,N′-di(2,6-diisopropylphenyl)-1,4-diazabutadienyl radical-anion, 2), in which active Y–H bonds were retained, while 1 reacted with PhC(O)Cy to yield a Y–H bond insertion product [(DAD)Y(μ-OC(H)PhCy)]2 (3). Complex 3 further reacted with PhC(O)Cy and lithium metal to give a C–C coupled product (DAD′)Y(PhCyC(O)C(O)PhCy)(OC(H)PhCy)Li(THF) (4). An investigation of the scope of reactivity of 1 found it reacted with PhN[double bond, length as m-dash]NPh to produce a two-electron reduced product (DAD′Y)2(μ-N(Ph)NPh)2(THF) (5), accompanied by the elimination of H2. The reaction of 1 with acridine afforded two structurally characterized yttrium 9-H acridinyl complexes (DAD)Y(NC13H10)(THF)2 (6) and (DAD′)Y(NC13H10)2(THF) (7). Investigations into the reactivity of 2 showed that 2 facilely reacted with PhC[triple bond, length as m-dash]CH to give an unusual hydride H and radical-anionic DAD ligand coupled product (DAD)Y(μ-Ph2C(O)C(O)Ph2)(μ-η21-C[triple bond, length as m-dash]CPh)Y(HDAD) (8), while 2 reacted with Me3SiC[triple bond, length as m-dash]CH to afford the mono Me3SiC[triple bond, length as m-dash]CH protolysis product (DAD′)Y(μ-Ph2C(O)C(O)Ph2)(C[triple bond, length as m-dash]CSiMe3)(μ-H)Y(DAD′) (9), in which no hydride H migration occurred. These results indicated that the electronic properties of the reductive DAD ligand strongly modified the reactivity of rare-earth hydrides.

Graphical abstract: Tuning rare-earth hydride reactivity with a reductive diazabutadienyl ligand beyond insertion

Supplementary files

Article information

Article type
Research Article
Submitted
15 Feb 2024
Accepted
23 Mai 2024
First published
24 Mai 2024

Inorg. Chem. Front., 2024,11, 3799-3810

Tuning rare-earth hydride reactivity with a reductive diazabutadienyl ligand beyond insertion

X. Lin, J. Zhang and X. Zhou, Inorg. Chem. Front., 2024, 11, 3799 DOI: 10.1039/D4QI00412D

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