Carbene derivatives of Ir4(CO)12]. Crystal structures of [Ir4(CO)12−x()x] (x=1, 2, 3)

Bondietti, Giacomo; Ros, Renzo; Roulet, Raymond; Musso, Fabrizio; Gervasio, Giuliana

doi:10.1016/s0020-1693(00)83840-2

Cited by 15 publications

(4 citation statements)

References 22 publications

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“…As far as we are aware, no transition metal cluster complexes containing N,O-heterocyclic carbenes have been previously described. However, a few examples of tetranuclear iridium and trinuclear ruthenium and osmium carbonyl clusters having O-heterocyclic carbenes have been reported. They all contain 1,3-dioxacyclopentan-2-ylidene that arises from the coupling of ethylene oxide with a coordinated CO ligand.…”

Section: Resultsmentioning

confidence: 99%

Reactivity of N-Heterocyclic Carbenes with [Ru₃(CO)₁₂] and [Os₃(CO)₁₂]. Influence of Ligand Volume and Electronic Effects

et al. 2007

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The room-temperature reactions of [Ru 3 (CO) 12 ] and [Os 3 (CO) 12 ] with a variety of N-heterocyclic carbenes (NHCs) have been studied. [Ru 3 (CO) 12 ] reacts easily with N,N′-dimethylimidazol-2-ylidene (Me 2 Im), more slowly with N-methyloxazol-2-ylidene (MeOx), and very slowly with N,N′-dimesitylimidazol-2-ylidene (Mes 2 Im) to give the corresponding CO substitution products [Ru 3 (NHC)(CO) 11 ], but it does not react with the very bulky N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Dipph 2 Im). DFT calculations have shown that [Ru 3 (Dipph 2 Im)(CO) 11 ] is a minimum in the corresponding potential energy surface; therefore, the absence of reaction between [Ru 3 (CO) 12 ] and Dipph 2 Im has a kinetic origin associated with the large volume of this NHC. [Os 3 (CO) 12 ] reacts with Me 2 Im to give [Os 3 (Me 2 Im)(CO) 11 ]. However, MeOx is not basic enough and Mes 2 Im and Dipph 2 Im are too bulky to react with [Os 3 (CO) 12 ], which is less reactive than [Ru 3 (CO) 12 ]. Therefore, the reactions of [Ru 3 (CO) 12 ] and [Os 3 (CO) 12 ] with NHCs are strongly influenced by the electronic properties and steric demands of the NHCs and also by the intrinsic reactivity of the metal-carbonyls.

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Section: Resultsmentioning

confidence: 99%

Reactivity of N-Heterocyclic Carbenes with [Ru₃(CO)₁₂] and [Os₃(CO)₁₂]. Influence of Ligand Volume and Electronic Effects

et al. 2007

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“…Since then, the catalytic properties of NHC-metal complexes have been extensively exploited. ,− and were part of the work leading to recognition with the 2005 Nobel Prize in Chemistry. Although there has been prior work on NHC-Ir complexes, − research on tetrairidium clusters with carbene ligands is rare. , …”

Section: Introductionmentioning

confidence: 99%

Role of N-Heterocyclic Carbenes as Ligands in Iridium Carbonyl Clusters

et al. 2017

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The low-energy isomers of Ir(CO)(NHC) (x = 1, 2, 4) are investigated with density functional theory (DFT) and correlated molecular orbital theory at the coupled cluster CCSD(T) level. The structures, relative energies, ligand dissociation energies, and natural charges are calculated. The energies of tetrairidium cluster are predicted at the CAM-B3LYP level that best fit the CCSD(T) results compared with the other four functionals in the benchmark calculations. The NHC's behave as stronger σ donors compared with CO's and have higher ligand dissociation energies (LDEs). For smaller isomers, the increase in the LDEs of the CO's and the decrease in the LDEs of the NHC's as more NHC's are substituted for CO's are due to π-back-bonding and electron repulsion, whereas the trend of how the LDEs change for larger isomers is not obvious. We demonstrate a μ-CO resulting from the high electron density of the metal centers in these complexes, as the bridging CO's and the μ-CO's can carry more negative charge and stabilize the isomers. Comparison of calculations for a mixed tetrairidum cluster consisting of two calixarene-phosphine ligands and a single calixarene-NHC ligand in the basal plane demonstrated good agreement in terms of both the ligand substitution symmetry (C derived), as well as the infrared spectra. Similar comparisons were also performed between calculations and experiment for novel monosubstituted calixarene-NHC tetrairidium clusters.

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“…The hydrido-derivatives of Ir ) n ] (n = 1-3) derived from the nucleophilic attack of the coordinated CO ligands of Ir 4 (CO) 12 by oxirane. 5 The classical organometallic reactions used for the preparation of metal alkyls failed to give any well defined derivatives from Ir 4 (CO) 12 . An idea for obtaining new clusters with Ir-C bonds is therefore to deprotonate a methylene group which is part of a bidentate ligand already bonded to Ir and form an Ir-C bond by intramolecular displacement of carbon monoxide.…”

Section: Introductionmentioning

confidence: 99%

Bis(diphosphino)methanide and hydride derivatives of Ir4(CO)12

Detti

Lumini

Roulet

et al. 2000

J. Chem. Soc., Dalton Trans.

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The reaction of [Ir 4 (CO) 10 (µ-(Ph 2 P) 2 CH 2 )] with dried KOH forms [Ir 4 (CO) 10 (µ-(Ph 2 P) 2 CH)] Ϫ which subsequently converts into [Ir 4 (CO) 9 (µ 3 -(Ph 2 P) 2 CH)] Ϫ , a rare example of an Ir cluster with an Ir-C bond (average 2.274(8) Å). The same reaction with the weaker base 1,8-diazobicyclo[5.4.0]undec-7-ene or with K 2 CO 3 in wet CH 2 Cl 2 under CO affords the anion [HIr 4 (CO) 9 (µ-(Ph 2 P) 2 CH 2 )] Ϫ , a hydride-cluster with an unusually long Ir-H distance (2.08(6) Å at 90 K). Intramolecular CO scrambling is observed in CD 2 Cl 2 solution above 200 K, preserving the terminal-axial position of the hydride ligand.

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Carbene derivatives of Ir4(CO)12]. Crystal structures of [Ir4(CO)12−x()x] (x=1, 2, 3)

Cited by 15 publications

References 22 publications

Reactivity of N-Heterocyclic Carbenes with [Ru₃(CO)₁₂] and [Os₃(CO)₁₂]. Influence of Ligand Volume and Electronic Effects

Reactivity of N-Heterocyclic Carbenes with [Ru₃(CO)₁₂] and [Os₃(CO)₁₂]. Influence of Ligand Volume and Electronic Effects

Role of N-Heterocyclic Carbenes as Ligands in Iridium Carbonyl Clusters

Bis(diphosphino)methanide and hydride derivatives of Ir4(CO)12

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Carbene derivatives of Ir4(CO)12]. Crystal structures of [Ir4(CO)12−x()x] (x=1, 2, 3)

Cited by 15 publications

References 22 publications

Reactivity of N-Heterocyclic Carbenes with [Ru3(CO)12] and [Os3(CO)12]. Influence of Ligand Volume and Electronic Effects

Reactivity of N-Heterocyclic Carbenes with [Ru3(CO)12] and [Os3(CO)12]. Influence of Ligand Volume and Electronic Effects

Role of N-Heterocyclic Carbenes as Ligands in Iridium Carbonyl Clusters

Bis(diphosphino)methanide and hydride derivatives of Ir4(CO)12

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Reactivity of N-Heterocyclic Carbenes with [Ru₃(CO)₁₂] and [Os₃(CO)₁₂]. Influence of Ligand Volume and Electronic Effects

Reactivity of N-Heterocyclic Carbenes with [Ru₃(CO)₁₂] and [Os₃(CO)₁₂]. Influence of Ligand Volume and Electronic Effects