IMes-acac: hybrid combination of diaminocarbene and acetylacetonato sub-units into a new anionic ambidentate NHC ligand

César, Vincent; Mallardo, Valentina; Nano, Adela; Dahm, Georges; Lugan, Noël; Lavigne, Guy; Bellemin‐Laponnaz, Stéphane

doi:10.1039/c4cc08641d

Cited by 52 publications

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“…Variety of reported transition metal polymetallic complexes supported by ambidentate and hybrid NHC ligands and preliminary results on the IMes-acetylacetonate (acac) ligand reported in our previous communication. 23 IPr = 1,3-bis(2,6-diisopropylphenyl)-2 H -imidazole-2-ylidene.…”

Section: Introductionmentioning

confidence: 99%

“…In 2015, we introduced the new anionic, hybrid 5-acetylimidazol-2-ylidene-4-olate 1 – , named as “IMes-acac”, constituted of fused diaminocarbene and acetylacetonato units in the same imidazolyl ring (Figure 1). 23 At that time, we reported the straightforward synthesis of its mesoionic precursor 1 ·H, through acetylation of the corresponding 4-hydroxyimidazolium chloride, its generation as a free, stable NHC, and demonstrated its ambidentate character through preliminary coordination studies using the [(IPr)Cu] + metallic fragment, leading to complexes L , M , and N . We report herein a complete, extended study on the coordination behavior of ligand 1 – toward various metallic centers and coordination geometries (Ru, Rh, Cu, and Au), and on the electronic structure of the resulting complexes, with an emphasis on the possible electronic interaction between both coordinating units within the ligand framework.…”

Section: Introductionmentioning

confidence: 99%

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Homo- and Heteropolymetallic Complexes of the Hybrid, Ambidentate N-Heterocyclic Carbene Ligand IMes-acac

et al. 2018

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The anionic 5-acetylimidazol-2-ylidene-4-olate 1 – , named as “IMes-acac”, is composed of fused diaminocarbene and acetylacetonato units in the same IMes-based imidazolyl ring. The bifunctional compound 1 – is shown to act as an effective, ditopic bridging ligand for transition metal centers. Several new complexes supported by this ligand were prepared, including the complex [RuCl( p -Cym)(κ 2 O , O – 1 ·H)](BF 4 ) ( 2 ), which can be regarded as a metallated imidazolium salt, the homobimetallic complex [((COD)Rh)(RhCl(COD))(μ-1κ 2 O , O :2κ 1 C – 1 )] ( 4 ), the heterobimetallic complexes [(( p -Cym)ClRu)(RhCl(COD))(μ-1κ 2 O , O :2κ 1 C – 1 )] ( 3 ), [(( p -Cym)ClRu)(RhCl(CO) 2 )(μ-1κ 2 O , O: 2κ 1 C – 1 )] ( 5 ), [(( p -Cym)ClRu)(Cu(IPr))(μ-1κ 2 O , O :2κ 1 C – 1 )] ( 9 ), the anionic homoleptic Cu(I) complexes [Cu(κ 1 C – 1 ) 2 ]K ([ 10 ]K) and [Cu(κ 1 C – 1 ) 2 ](NEt 4 ) ([ 10 ](NEt 4 )), and the heterotrimetallic complex [(( p -Cym)RuCl) 2 (Cu)(μ-1κ 2 O , O :3κ 1 C – 1 )(μ-2κ 2 O , O :3κ 1 C – 1 )](PF 6 ) ( 11 ). Preliminary studies on the possible preparation of supramolecular metallopolymers and electrochemical studies on the series of complexes are also reported.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Homo- and Heteropolymetallic Complexes of the Hybrid, Ambidentate N-Heterocyclic Carbene Ligand IMes-acac

et al. 2018

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“…An alternative to halide or amide ligands would be the use of anionic carbenes, based on imidazolylidene‐type NHC carbenes which possess on their backbone a moiety bearing an anionic charge while being π‐conjugated to the NHC moiety . This family of ligands has been intensively studied, and some of them were used to stabilise group 11 metal ions . Anionic 6‐ring NHC ligands based on a malonate unit ( malo NHC ) , have also been developed and coordinated to silver and to gold halide and phosphane complexes, including reports on copper halide and copper bis(carbene) complexes .…”

Section: Introductionmentioning

confidence: 99%

Zwitterionic Mixed‐Carbene Coinage Metal Complexes: Synthesis, Structures, and Photophysical Studies

et al. 2019

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A series of three zwitterionic mixed-ligand bis-(carbene) complexes of copper (1), silver (2) and gold (3) have been synthesized, based on a combination of ethyl-substituted cyclic (alkyl)(amino)carbene ( Et2 CAAC) and an anionic methylmalonate-derived N-heterocyclic carbene (maloNHC). The crystal structures confirm the linear two-coordinate geometry without close intermolecular contacts. The compounds show blue-[a] 4234 [a] Cyclic voltammograms recorded in THF solution (1.4 mM) at 0.1 V s -1 using a glassy carbon electrode, with [nBu 4 N][PF 6 ] (0.13 M) as supporting electrolyte.

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“…The anionic N-heterocyclic carbene 3 is substituted by a siliconate group at C4 8 and the corresponding boron derivatives belong to a similar molecular architecture. 9 The anions 4 10 and 5 11 were prepared by deprotonation of conjugated mesomeric betaines (CMB), i.e. imidazolium-olates and sydnones, respectively.…”

Section: Introductionmentioning

confidence: 99%

Purine-substituted imidazolium mesomeric betaines and their tautomeric N-heterocyclic carbenes. Formation of a cyclic borane adduct

et al. 2018

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6-Chloropurine and 2,6-dichloropurine were reacted with N1-substituted imidazoles to give purin-6-yl substituted imidazolium salts, respectively. Deprotonation of the 1-methylimidazolium derivative resulted in the formation of the corresponding stable conjugated mesomeric betaine, whereas the 1-phenyl,- 1-vinyl- and 1-(2-hydroxyethyl) derivatives proved to be unstable. In situ generation of the mesomeric betaines by caesium carbonate in the presence of sulfur and selenium, however, gave the thiones and the selenones of the tautomeric purine-substituted imidazol-2-ylidene, respectively. Its anionic N-heterocyclic carbene was formally trapped by reaction with triethylborane at high temperatures as a cyclic boron adduct which is the first representative of a new heterocyclic ring system. DFT calculations gained insight into the electronic properties of the N-heterocyclic carbenes substituted by π-electron donators. Results of a single crystal X-ray analysis of the boron adduct are presented.

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IMes-acac: hybrid combination of diaminocarbene and acetylacetonato sub-units into a new anionic ambidentate NHC ligand

Cited by 52 publications

References 44 publications

Homo- and Heteropolymetallic Complexes of the Hybrid, Ambidentate N-Heterocyclic Carbene Ligand IMes-acac

Homo- and Heteropolymetallic Complexes of the Hybrid, Ambidentate N-Heterocyclic Carbene Ligand IMes-acac

Zwitterionic Mixed‐Carbene Coinage Metal Complexes: Synthesis, Structures, and Photophysical Studies

Purine-substituted imidazolium mesomeric betaines and their tautomeric N-heterocyclic carbenes. Formation of a cyclic borane adduct

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