Versatility of a diamidosilylether ligand supporting yttrium complexes: Synthesis, structure and reactivity

Mathew D. Anker; Matthew J. Evans; Scott A. Cameron; Geoffry Laufersky

doi:10.1016/j.poly.2023.116741

Versatility of a diamidosilylether ligand supporting yttrium complexes: Synthesis, structure and reactivity

Mathew D. Anker, Matthew J. Evans, Scott A. Cameron, Geoffry Laufersky

Research output: Contribution to journal › Article › Research › peer-review

Abstract

Yttrium alkyl complex [NON^DippY(CH₂SiMe₃)(THF)], 1 (NON^Dipp = (DippNSiMe₂)₂O, Dipp = 2,6-ⁱPr-C₆H₃) can be prepared in high yields by a σ-bond metathesis reaction between [Y(CH₂SiMe₃)₃(THF)₂] and the free bis(aminosilyl)ether. The reaction of 1 with one equivalent of PhSiH₃ generates the hydride bridged yttrium dimer [μ-NON^DippY(μ-H)(THF)]₂ 2, however, each diamidosilylether ligand does not chelate each yttrium centre but instead bridges to both yttrium atoms in a “flyover” fashion. This ligand rearrangement maybe reversed by the addition of a strong Lewis base to give the dimeric yttrium hydride [NON^DippY(μ-H)(DMAP)]₂ 3, where each diamidosilylether ligand now chelate to each yttrium center respectively. The effect of the different diamidosilylether bonding modes on the reactivity of the yttrium complexes is examined with heterocumulenes.

Original language	English
Article number	116741
Number of pages	9
Journal	Polyhedron
Volume	247
DOIs	https://doi.org/10.1016/j.poly.2023.116741
Publication status	Published - 1 Jan 2024
Externally published	Yes

Keywords

Flyover dimer
Metal hydrides
Yttrium alkyl
Yttrium hydride

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10.1016/j.poly.2023.116741Licence: CC BY

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title = "Versatility of a diamidosilylether ligand supporting yttrium complexes: Synthesis, structure and reactivity",

abstract = "Yttrium alkyl complex [NONDippY(CH2SiMe3)(THF)], 1 (NONDipp = (DippNSiMe2)2O, Dipp = 2,6-iPr-C6H3) can be prepared in high yields by a σ-bond metathesis reaction between [Y(CH2SiMe3)3(THF)2] and the free bis(aminosilyl)ether. The reaction of 1 with one equivalent of PhSiH3 generates the hydride bridged yttrium dimer [μ-NONDippY(μ-H)(THF)]2 2, however, each diamidosilylether ligand does not chelate each yttrium centre but instead bridges to both yttrium atoms in a “flyover” fashion. This ligand rearrangement maybe reversed by the addition of a strong Lewis base to give the dimeric yttrium hydride [NONDippY(μ-H)(DMAP)]2 3, where each diamidosilylether ligand now chelate to each yttrium center respectively. The effect of the different diamidosilylether bonding modes on the reactivity of the yttrium complexes is examined with heterocumulenes.",

keywords = "Flyover dimer, Metal hydrides, Yttrium alkyl, Yttrium hydride",

author = "Anker, {Mathew D.} and Evans, {Matthew J.} and Cameron, {Scott A.} and Geoffry Laufersky",

note = "Publisher Copyright: {\textcopyright} 2023 The Authors",

year = "2024",

month = jan,

day = "1",

doi = "10.1016/j.poly.2023.116741",

language = "English",

volume = "247",

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T1 - Versatility of a diamidosilylether ligand supporting yttrium complexes

T2 - Synthesis, structure and reactivity

AU - Anker, Mathew D.

AU - Evans, Matthew J.

AU - Cameron, Scott A.

AU - Laufersky, Geoffry

PY - 2024/1/1

Y1 - 2024/1/1

N2 - Yttrium alkyl complex [NONDippY(CH2SiMe3)(THF)], 1 (NONDipp = (DippNSiMe2)2O, Dipp = 2,6-iPr-C6H3) can be prepared in high yields by a σ-bond metathesis reaction between [Y(CH2SiMe3)3(THF)2] and the free bis(aminosilyl)ether. The reaction of 1 with one equivalent of PhSiH3 generates the hydride bridged yttrium dimer [μ-NONDippY(μ-H)(THF)]2 2, however, each diamidosilylether ligand does not chelate each yttrium centre but instead bridges to both yttrium atoms in a “flyover” fashion. This ligand rearrangement maybe reversed by the addition of a strong Lewis base to give the dimeric yttrium hydride [NONDippY(μ-H)(DMAP)]2 3, where each diamidosilylether ligand now chelate to each yttrium center respectively. The effect of the different diamidosilylether bonding modes on the reactivity of the yttrium complexes is examined with heterocumulenes.

AB - Yttrium alkyl complex [NONDippY(CH2SiMe3)(THF)], 1 (NONDipp = (DippNSiMe2)2O, Dipp = 2,6-iPr-C6H3) can be prepared in high yields by a σ-bond metathesis reaction between [Y(CH2SiMe3)3(THF)2] and the free bis(aminosilyl)ether. The reaction of 1 with one equivalent of PhSiH3 generates the hydride bridged yttrium dimer [μ-NONDippY(μ-H)(THF)]2 2, however, each diamidosilylether ligand does not chelate each yttrium centre but instead bridges to both yttrium atoms in a “flyover” fashion. This ligand rearrangement maybe reversed by the addition of a strong Lewis base to give the dimeric yttrium hydride [NONDippY(μ-H)(DMAP)]2 3, where each diamidosilylether ligand now chelate to each yttrium center respectively. The effect of the different diamidosilylether bonding modes on the reactivity of the yttrium complexes is examined with heterocumulenes.

KW - Flyover dimer

KW - Metal hydrides

KW - Yttrium alkyl

KW - Yttrium hydride

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DO - 10.1016/j.poly.2023.116741

M3 - Article

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JO - Polyhedron

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ER -

Versatility of a diamidosilylether ligand supporting yttrium complexes: Synthesis, structure and reactivity

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Keywords

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