Synthesis and molecular structure of an abnormal carbene–gallium chloride complex

Chen, Mingwei; Wang, Yu‐Zhong; Gilliard, Robert J.; Wei, Pingrong; Schwartz, Nichole A.; Robinson, Gregory H.

doi:10.1039/c4dt00933a

Cited by 14 publications

(24 citation statements)

References 41 publications

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“…[14] Accessing an abnormalNHC-Mgcomplex via electrophilic interception Withinm ain group chemistry,t he number of complexesc ontaininga bnormal (or mesoionic) carbenes remains very limited, and for Mg the first examples containing this type of ligands were only reported in 2016 by Ghadwall. Having successfully isolated anionic NHC complex 2 we next pondered, if it could undergo selective electrophilic interception to render the relevant neutral aNHC-Mg complex, as this approach has already shown promising potentialf or other main group elements including B, [31] Ga [22,27,32] andZ n. [33] To explore this possibility sodiumm agnesiate 2 was treated with amolar equivalent of Me 3 SiCl in toluene at À30 8C. Our previous attemptt o access aIPr·MgR 2 by employing thermally induced isomerization of its normal analogue (i.e.…”

Section: Resultsmentioning

confidence: 99%

Molecular Manipulations of a Utility Nitrogen–Heterocyclic Carbene by Sodium Magnesiate Complexes and Transmetallation Chemistry with Gold Complexes

Hernán‐Gómez

Uzelac

Baillie

et al. 2018

Chemistry A European J

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Expanding the scope and applications of anionic N-heterocyclic carbenes (NHCs), a novel series of magnesium NHC complexes is reported using a mixed sodium-magnesium approach. Sequential reactivity of classical imidazol- 2-ylidene carbene IPr with NaR and MgR (R=CH SiMe ) affords [(THF) Na(μ-IPr )MgR (THF)] (2) [IPr =:C{[N(2,6-iPr C H )] CHC] containing an anionic NHC ligand, whereas surprisingly sodium magnesiate [NaMgR ] fails to deprotonate IPr affording instead the redistribution coordination adduct [IPr Na MgR ] (1). Compound 2 undergoes selective C2-methylation when treated with MeOTf furnishing novel abnormal NHC complex [{aIPr MgR } ] (3). Dissolving 3 in THF led to the dissociation of this complex into MgR and aIPr with the latter isomerizing to the olefinic NHC IPr=CH . The ability of 2 and 3 to transfer their anionic and abnormal NHC ligands, respectively to Au metal fragments has been investigated allowing the isolation and structural characterization of [RAu(μ-IPr )MgR(THF) ] (4) and [aIPr AuR] (5) respectively. In both cases transfer of an alkyl R group is observed. However while 3 can also transfer its abnormal NHC ligand to give 5, in 4 the anionic NHC still remains coordinated to Mg via its C4 position, whereas the {AuR} fragment occupies the C2 position previously filled by a donor-solvated {Na(THF) } cation.

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Section: Resultsmentioning

confidence: 99%

Molecular Manipulations of a Utility Nitrogen–Heterocyclic Carbene by Sodium Magnesiate Complexes and Transmetallation Chemistry with Gold Complexes

Hernán‐Gómez

Uzelac

Baillie

et al. 2018

Chemistry A European J

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“…26). However, Robinson and co-workers were able to target the "normally" bound anionic IPr-BEt 3 complex 50 using a similar method to that employed by Roesky and co-workers when synthesizing the equivalent anionic IPr-BH 3 complex [119,120]. Addition of n BuLi to the neutral carbene-borane adducts in THF serves to deprotonate the backbone and no reorganization of the borane moiety is observed.…”

Section: Group 13 Complexes Of Ditopic Carbanionic Carbenesmentioning

confidence: 89%

“…Nevertheless, heating 50 will drive the formation of the thermodynamic product 49. This allows for functionalization at the C2 or C4 position as demonstrated by the reactions of 49 and 50 with GaCl 3 [119].…”

Section: Group 13 Complexes Of Ditopic Carbanionic Carbenesmentioning

confidence: 97%

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Coordination chemistry of ditopic carbanionic N-heterocyclic carbenes

Waters

Goicoechea

2015

Coordination Chemistry Reviews

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“…Aluminates, 6 gallates, 7 and other species also belong to this type of N-heterocyclic carbenes. Carbenes with one or more coordinating tethered anionic ligands such as 2 can also be termed zwitterionic anionic N-heterocyclic carbenes, because the sp 3hybridized carbon atoms interrupt the conjugation between carbene and anionic moieties.…”

Section: Scheme 1 Examples Of Zwitterionic Anionic N-heterocyclic Camentioning

confidence: 99%

Anionic N-heterocyclic carbenes by decarboxylation of sydnone-4-carboxylates

et al. 2018

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Unstable N-heterocyclic carbenes can be masked and stabilized as pseudo-cross-conjugated hetarenium-carboxylates which decarboxylate on warming. This study deals with the decarboxylation of carboxylates of mesoionic compounds to generate anionic N-heterocyclic carbenes. Lithium sydnone-4-carboxylates were therefore prepared via 4-bromosydnones by halogen-lithium exchange with nBuLi and subsequent treatment with carbon dioxide. Protonation gave the corresponding sydnone-4-carboxylic acids. Thermogravimetric measurements in addition to temperature dependent IR spectroscopy proved the decarboxylation of lithium sydnone-4-carboxylates and formation of the corresponding sydnone anions which can be represented as anionic N-heterocyclic carbenes. In DMSO-d6 solution, water favors the decarboxylation. Calculations have been performed to elucidate the mechanism of the decarboxylation in the absence and presence of water.

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Synthesis and molecular structure of an abnormal carbene–gallium chloride complex

Cited by 14 publications

References 41 publications

Molecular Manipulations of a Utility Nitrogen–Heterocyclic Carbene by Sodium Magnesiate Complexes and Transmetallation Chemistry with Gold Complexes

Molecular Manipulations of a Utility Nitrogen–Heterocyclic Carbene by Sodium Magnesiate Complexes and Transmetallation Chemistry with Gold Complexes

Coordination chemistry of ditopic carbanionic N-heterocyclic carbenes

Anionic N-heterocyclic carbenes by decarboxylation of sydnone-4-carboxylates

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