The Synthesis and Structure of Pentacarbonyl (5<i>H</i>‐dipyrrolo[1,2‐<i>c</i>: 2′,1′‐e]imidazol‐5‐yl)manganese

Bürger, Ulrich; Perret, C.; Bérnardinelli, Gerald; Kündig, E. Peter

doi:10.1002/hlca.19840670806

Cited by 6 publications

(1 citation statement)

References 23 publications

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“…In both cases, the chloride ligand contributes to the stabilization of the complex. It is noteworthy that the preference for alkyl versus NHC coordination has been rarely encountered in structurally characterized examples (Zr, [93] Mn, [94] Ni, [95,96] Pd, [62,97,98] and Ir [76] ).…”

Section: Chemistry-a European Journalmentioning

confidence: 99%

Experimental and Theoretical Study of Ni^II‐ and Pd^II‐Promoted Double Geminal C(sp³)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism

Gourlaouen

Pang

et al. 2022

Chemistry A European J

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We report the first examples of metal-promoted double geminal activation of C(sp 3 )À H bonds of the NÀ CH 2 À N moiety in an imidazole-type heterocycle, leading to nickel and palladium N-heterocyclic carbene complexes under mild conditions. Reaction of the new electron-rich diphosphine 1,3-bis((di-tert-butylphosphaneyl)methyl)-2,3-dihydro-1Hbenzo[d]imidazole (1) with [PdCl 2 (cod)] occurred in a stepwise fashion, first by single CÀ H bond activation yielding the alkyl pincer complex [PdCl(PC sp 3 H P)] (3) with two trans phosphane donors and a covalent PdÀ C sp 3 bond. Activation of the CÀ H bond of the resulting α-methine C sp 3 HÀ M group occurred subsequently when 3 was treated with HCl to yield the NHC pincer complex [PdCl(PC NHC P)]Cl (2). Treatment of 1 with [NiBr 2 (dme)] also afforded a NHC pincer complex, [NiBr(PC NHC P)]Br ( 6), but the reactions leading to the double geminal CÀ H bond activation of the NÀ CH 2 À N group were too fast to allow identification or isolation of an intermediate analogous to 3. The determination of six crystal structures, the isolation of reaction intermediates and DFT calculations provided the basis for suggesting the mechanism of the stepwise transformation of a NÀ CH 2 À N moiety in the NÀ C NHC À N unit of NHC pincer complexes and explain the key differences observed between the Pd and Ni chemistries.

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Section: Chemistry-a European Journalmentioning

confidence: 99%

Experimental and Theoretical Study of Ni^II‐ and Pd^II‐Promoted Double Geminal C(sp³)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism

Gourlaouen

Pang

et al. 2022

Chemistry A European J

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Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium

et al. 2015

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A Ni0‐NCN pincer complex featuring a six‐membered N‐heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its NiII precursor. It retained chloride in the square‐planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni0 complex rapidly activated ammonia at room temperature, in a ligand‐assisted process where the carbene carbon atom played the unprecedented role of proton acceptor. For the first time, the coordinated (ammine) and activated (amido) species were observed together in solution, in a solvent‐dependent equilibrium. A structural analysis of the Ni complexes provided insight into the highly unusual, non‐innocent behavior of the NHC ligand.

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Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium

et al. 2015

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The Synthesis and Structure of Pentacarbonyl (5H‐dipyrrolo[1,2‐c: 2′,1′‐e]imidazol‐5‐yl)manganese

Cited by 6 publications

References 23 publications

Experimental and Theoretical Study of Ni^II‐ and Pd^II‐Promoted Double Geminal C(sp³)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism

Experimental and Theoretical Study of Ni^II‐ and Pd^II‐Promoted Double Geminal C(sp³)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism

Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium

Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium

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The Synthesis and Structure of Pentacarbonyl (5H‐dipyrrolo[1,2‐c: 2′,1′‐e]imidazol‐5‐yl)manganese

Cited by 6 publications

References 23 publications

Experimental and Theoretical Study of NiII‐ and PdII‐Promoted Double Geminal C(sp3)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism

Experimental and Theoretical Study of NiII‐ and PdII‐Promoted Double Geminal C(sp3)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism

Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium

Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium

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Experimental and Theoretical Study of Ni^II‐ and Pd^II‐Promoted Double Geminal C(sp³)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism

Experimental and Theoretical Study of Ni^II‐ and Pd^II‐Promoted Double Geminal C(sp³)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism