Ga–C and Ga–Ga bond formation using a NON-ligated gallyl nucleophile

Megan Edwards; Jamie Hicks; Caitilín McManus; Jose M. Goicoechea; Simon Aldridge

doi:10.1016/j.poly.2023.116520

Ga–C and Ga–Ga bond formation using a NON-ligated gallyl nucleophile

Megan Edwards, Jamie Hicks, Caitilín McManus, Jose M. Goicoechea^*, Simon Aldridge

^*Corresponding author for this work

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

Abstract

We report an improved synthesis of the NON-donor stabilized potassium gallyl dimer [K{Ga(NON)}]₂ (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene) from (NON)GaI and potassium naphthalenide that avoids issues associated with over-reduction of the metal centre. The use of [K{Ga(NON)}]₂ in the synthesis of Ga–E bonds has been explored through its reactions with a range of electrophiles. The reaction with (NON)GaI to give {Ga(NON)}₂ via Ga–Ga bond formation mirrors the behaviour of the corresponding aluminyl compound, while Ga–C bond formation via nucleophilic attack on 1-bromopentane to give (NON)Ga(n-pentyl) avoids the retention of KBr often encountered in the formation of (more Lewis acidic) Al^III compounds. Attempted formation of a Mg–Ga bond, e.g. via the reaction of [K{Ga(NON)}]₂ with (Nacnac^Mes)MgI(OEt₂), generates instead the unsymmetrical digallane(4), (Nacnac^Mes)Ga(μ₂-N,N'-NON)GaI, consistent with enhanced lability of Ga (over Al) within the NON-ligand scaffold.

Original language	English
Article number	116520
Journal	Polyhedron
Volume	242
DOIs	https://doi.org/10.1016/j.poly.2023.116520
Publication status	Published - 15 Sept 2023
Externally published	Yes

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@article{f42b7b8619264ec0983c515a929471c3,

title = "Ga–C and Ga–Ga bond formation using a NON-ligated gallyl nucleophile",

abstract = "We report an improved synthesis of the NON-donor stabilized potassium gallyl dimer [K{Ga(NON)}]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene) from (NON)GaI and potassium naphthalenide that avoids issues associated with over-reduction of the metal centre. The use of [K{Ga(NON)}]2 in the synthesis of Ga–E bonds has been explored through its reactions with a range of electrophiles. The reaction with (NON)GaI to give {Ga(NON)}2 via Ga–Ga bond formation mirrors the behaviour of the corresponding aluminyl compound, while Ga–C bond formation via nucleophilic attack on 1-bromopentane to give (NON)Ga(n-pentyl) avoids the retention of KBr often encountered in the formation of (more Lewis acidic) AlIII compounds. Attempted formation of a Mg–Ga bond, e.g. via the reaction of [K{Ga(NON)}]2 with (NacnacMes)MgI(OEt2), generates instead the unsymmetrical digallane(4), (NacnacMes)Ga(μ2-N,N'-NON)GaI, consistent with enhanced lability of Ga (over Al) within the NON-ligand scaffold.",

keywords = "Gallium, Gallyl, Metal–metal bond, Nucleophile",

author = "Megan Edwards and Jamie Hicks and Caitil{\'i}n McManus and Goicoechea, {Jose M.} and Simon Aldridge",

note = "Publisher Copyright: {\textcopyright} 2023 The Author(s)",

year = "2023",

month = sep,

day = "15",

doi = "10.1016/j.poly.2023.116520",

language = "English",

volume = "242",

journal = "Polyhedron",

issn = "0277-5387",

publisher = "Elsevier Ltd.",

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TY - JOUR

T1 - Ga–C and Ga–Ga bond formation using a NON-ligated gallyl nucleophile

AU - Edwards, Megan

AU - Hicks, Jamie

AU - McManus, Caitilín

AU - Goicoechea, Jose M.

AU - Aldridge, Simon

PY - 2023/9/15

Y1 - 2023/9/15

N2 - We report an improved synthesis of the NON-donor stabilized potassium gallyl dimer [K{Ga(NON)}]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene) from (NON)GaI and potassium naphthalenide that avoids issues associated with over-reduction of the metal centre. The use of [K{Ga(NON)}]2 in the synthesis of Ga–E bonds has been explored through its reactions with a range of electrophiles. The reaction with (NON)GaI to give {Ga(NON)}2 via Ga–Ga bond formation mirrors the behaviour of the corresponding aluminyl compound, while Ga–C bond formation via nucleophilic attack on 1-bromopentane to give (NON)Ga(n-pentyl) avoids the retention of KBr often encountered in the formation of (more Lewis acidic) AlIII compounds. Attempted formation of a Mg–Ga bond, e.g. via the reaction of [K{Ga(NON)}]2 with (NacnacMes)MgI(OEt2), generates instead the unsymmetrical digallane(4), (NacnacMes)Ga(μ2-N,N'-NON)GaI, consistent with enhanced lability of Ga (over Al) within the NON-ligand scaffold.

AB - We report an improved synthesis of the NON-donor stabilized potassium gallyl dimer [K{Ga(NON)}]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethyl-xanthene) from (NON)GaI and potassium naphthalenide that avoids issues associated with over-reduction of the metal centre. The use of [K{Ga(NON)}]2 in the synthesis of Ga–E bonds has been explored through its reactions with a range of electrophiles. The reaction with (NON)GaI to give {Ga(NON)}2 via Ga–Ga bond formation mirrors the behaviour of the corresponding aluminyl compound, while Ga–C bond formation via nucleophilic attack on 1-bromopentane to give (NON)Ga(n-pentyl) avoids the retention of KBr often encountered in the formation of (more Lewis acidic) AlIII compounds. Attempted formation of a Mg–Ga bond, e.g. via the reaction of [K{Ga(NON)}]2 with (NacnacMes)MgI(OEt2), generates instead the unsymmetrical digallane(4), (NacnacMes)Ga(μ2-N,N'-NON)GaI, consistent with enhanced lability of Ga (over Al) within the NON-ligand scaffold.

KW - Gallium

KW - Gallyl

KW - Metal–metal bond

KW - Nucleophile

UR - http://www.scopus.com/inward/record.url?scp=85166750918&partnerID=8YFLogxK

U2 - 10.1016/j.poly.2023.116520

DO - 10.1016/j.poly.2023.116520

M3 - Article

AN - SCOPUS:85166750918

SN - 0277-5387

VL - 242

JO - Polyhedron

JF - Polyhedron

M1 - 116520

ER -

Ga–C and Ga–Ga bond formation using a NON-ligated gallyl nucleophile

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