Heterobimetallic Carbene Complexes by a Single-Step Site-Selective Metalation of a Tricarbene Ligand

Maity, Ramananda; Koppetz, Hannah; Hepp, Alexander; Hahn, F. Ekkehardt

doi:10.1021/ja401546h

Cited by 91 publications

(61 citation statements)

References 51 publications

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“…The Ir-C bond length is identical within esd's in both complexes, 2.034(5) Å and 2.036(2) Å, respectively (Table 1). This distance is similar to related iridium NHC complexes [30,[60][61][62][63][64]. The piano-stool geometry is slightly flatter in the iodide complex 2b, as indicated by the consistently wider angles between the three "legs", while most of the angles involving the Cp* centroid are more acute than in the chloride analogue 2a.…”

Section: Resultssupporting

confidence: 79%

Iridium, ruthenium, and palladium complexes containing a mesoionic fused imidazolylidene ligand

Petronilho

Müeller-Bunz

Albrecht

2015

Journal of Organometallic Chemistry

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Imidazo[1,2-a]pyridine consisting of a pyridine fused to an imidazolium salt at the imidazolium N1-C2 bond and hence protected from forming normal imidazole-2-ylidene complexes undergoes selective activation of the C5-H bond with Ag 2 O, i.e. at the imidazolium carbon that is proximal to the pyridine nitrogen. While the silver carbene complex is unstable, transmetallation with [IrCp*Cl 2 ] 2 , [RuCl 2 (cym)] 2 , and [PdCl(allyl)] 2 afforded stable mesoionic carbene complexes. Two iridium(III) complexes containing one fused carbene ligand and one palladium(II) complex containing two carbene ligands at the metal center were structurally characterized. The absence of substituents adjacent to the carbene carbon prevents wingtip group activation, and it imparts a reduced stability of the complexes in particular under (mildly) acidic conditions.

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Section: Resultssupporting

confidence: 79%

Iridium, ruthenium, and palladium complexes containing a mesoionic fused imidazolylidene ligand

Petronilho

Müeller-Bunz

Albrecht

2015

Journal of Organometallic Chemistry

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“…It is more appropriate to term such a ring as a metallo‐macrocycle. The ligand showed differential coordination ability, under appropriate conditions and acted either as a bi‐ or tridentate ligand in a stoichiometrically controlled manner upon complexation with a calculated amount of Pd(NO 3 ) 2 (see Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Double‐Decker Coordination Cages

et al. 2016

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Bis(pyridin‐3‐ylmethyl) pyridine‐3,5‐dicarboxylate (L) possessing one internal and two terminal pyridine moieties displayed differential coordination ability when combined with suitable PdII components. The compound L acted as a bidentate chelating ligand to form mononuclear complexes when combined with cis‐[Pd(tmeda)(NO3)2] or Pd(NO3)2 in calculated ratios. The combination of Pd(NO3)2 with L in a ratio of 3:4, however, afforded the trinuclear “double‐decker” cage [(NO3)2⊂Pd3(L)4](NO3)4, in which L acts as a nonchelating tridentate ligand and the counter anion (i.e., NO3–) acts as template. The encapsulated NO3– can be replaced by F–, Cl–, or Br– but not by I–. The F–‐encapsulated cage could not be isolated due to its reactivity, whereas the Cl– or Br– encapsulated cages could be isolated. Although anionic guests such as NO3–, Cl–, or Br– stabilized the cages, the presence of excess Cl– or Br– (not NO3–) facilitated decomplexation reactions releasing the ligand. The complexation of Pd(Y)2 (Y = BF4–, PF6–, CF3SO3–, or ClO4–) with L afforded the corresponding mononuclear complexes under appropriate conditions. However, these counter anions could not act as templates for the construction of double‐decker cages.

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“…Recently, the single-step, site-selective metalation of a tricarbene ligand leading to complex E was also reported. [17] Regioselective metalation leading to complex E is based on differences in the coordination chemistry of Pd II and Ir III or Rh III , respectively. In this contribution, we present the stepwise metalation of a macrocyclic tetraimidazolium cation with two different metals again by utilizing differences in their coordination chemistry for the preparation of heterobimetallic complexes.…”

Section: Introductionmentioning

confidence: 99%

Trinuclear Heterobimetallic Complexes by Stepwise Metalation of a Macrocyclic Tetraimidazolium Salt

Brinke

Hahn

2015

Eur J Inorg Chem

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Five plus H2 gives four: UV irradiation of a bis(amidinate) complex with a [(H)MoMo(H)] core induces reductive elimination of H2 and formation of a known quintuply bonded MoMo species (see scheme) that reacts back with H2 to restore [(H)MoMo(H)]. UV irradiation of the bis(hydride) species in benzene and toluene gives arene complexes in which the aromatic hydrocarbon bridges the molybdenum atoms. Dipp=2,6‐diisopropylphenyl.

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Heterobimetallic Carbene Complexes by a Single-Step Site-Selective Metalation of a Tricarbene Ligand

Cited by 91 publications

References 51 publications

Iridium, ruthenium, and palladium complexes containing a mesoionic fused imidazolylidene ligand

Iridium, ruthenium, and palladium complexes containing a mesoionic fused imidazolylidene ligand

Double‐Decker Coordination Cages

Trinuclear Heterobimetallic Complexes by Stepwise Metalation of a Macrocyclic Tetraimidazolium Salt

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