Expedient Synthesis of Highly Functionalized Abnormal Carbenegold(I) Complexes

Flores-Jarillo, Mariana; Salazar‐Pereda, Verónica; Ruiz-Mendoza, Francisco Javier; Álvarez‐Hernández, Alejandro; Suárez‐Castillo, Oscar R.; Mendoza‐Espinosa, Daniel

doi:10.1021/acs.inorgchem.7b02774

Cited by 5 publications

(3 citation statements)

References 53 publications

(29 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…255 A similar procedure provides access to aNHC gold(I) complexes. 256 3.2.3. Isomerization from Free 2-Imidazolylidene Ligands.…”

Section: Synthesis Of Mesoionic Imidazolylidene Metal Complexesmentioning

confidence: 99%

“…The same protocol has also been applied for the in situ generation of a free mesoionic imidazolylidene from the tris(aryl)-substituted imidazolium salt 245 and subsequent metal coordination, which affords the aNHC copper(I) complex 271 (Scheme ). A similar procedure provides access to aNHC gold(I) complexes …”

Section: Complexes With Mesoionic Imidazolylidene Ligandsmentioning

confidence: 99%

See 1 more Smart Citation

Mesoionic and Related Less Heteroatom-Stabilized N-Heterocyclic Carbene Complexes: Synthesis, Catalysis, and Other Applications

2018

View full text Add to dashboard Cite

Mesoionic carbenes are a subclass of the family of N-heterocyclic carbenes that generally feature less heteroatom stabilization of the carbenic carbon and hence impart specific donor properties and reactivity schemes when coordinated to a transition metal. Therefore, mesoionic carbenes and their complexes have attracted considerable attention both from a fundamental point of view as well as for application in catalysis and beyond. As a follow-up of an earlier Chemical Reviews overview from 2009, the organometallic chemistry of N-heterocyclic carbenes with reduced heteroatom stabilization is compiled for the 2008-2017 period, including specifically the chemistry of complexes containing 1,2,3-triazolylidenes, 4-imidazolylidenes, and related 5-membered N-heterocyclic carbenes with reduced heteratom stabilization such as (is)oxazolylidenes, pyrrazolylidenes, and thiazolylidenes, as well as pyridylidenes as 6-membered N-heterocyclic carbenes with reduced heteroatom stabilization. For each ligand subclass, metalation strategies, electronic and steric properties, and applications, in particular, in metal-mediated catalysis, are compiled. Mesoionic carbenes demonstrate particularly high activity in (water) oxidation, hydrogen transfer reactions, and cyclization reactions. Unique features of these ligands are identified such as their dipolar structure, their specific donor properties, as well as stability aspects of the ligand and the complexes, which provides opportunities for further research.

show abstract

“…255 A similar procedure provides access to aNHC gold(I) complexes. 256 3.2.3. Isomerization from Free 2-Imidazolylidene Ligands.…”

Section: Synthesis Of Mesoionic Imidazolylidene Metal Complexesmentioning

confidence: 99%

Section: Complexes With Mesoionic Imidazolylidene Ligandsmentioning

confidence: 99%

Mesoionic and Related Less Heteroatom-Stabilized N-Heterocyclic Carbene Complexes: Synthesis, Catalysis, and Other Applications

2018

View full text Add to dashboard Cite

show abstract

“…1 The attempted development of ‘spectator’ ligands, often crucial for the optimization of catalytic processes, 2–4 is triggering continuing efforts to discover novel phosphine 5 or NHC ligand types with diverse and tuneable steric and electronic properties. Within the latter ligand class, in addition to the common C2-bound imidazol-2-ylidenes, other NHC ligands have emerged, including the abnormal imidazol-5-ylidenes (aNHC), the 1,2,3-triazolylidenes, 6,7 the cyclic (alkyl)(amino)carbenes (CAAC), 8–11 and the ring-expanded NHCs (reNHC) (Fig. 1).…”

mentioning

confidence: 99%

Gold complexes with remote-substituted amino N-heterocyclic carbenes

et al. 2023

View full text Add to dashboard Cite

show abstract

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

View full text Add to dashboard Cite

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.

show abstract

Expedient Synthesis of Highly Functionalized Abnormal Carbenegold(I) Complexes

Cited by 5 publications

References 53 publications

Mesoionic and Related Less Heteroatom-Stabilized N-Heterocyclic Carbene Complexes: Synthesis, Catalysis, and Other Applications

Mesoionic and Related Less Heteroatom-Stabilized N-Heterocyclic Carbene Complexes: Synthesis, Catalysis, and Other Applications

Gold complexes with remote-substituted amino N-heterocyclic carbenes

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

Contact Info

Product

Resources

About