Saturated N-heterocyclic Carbene Research Articles

Subvalent group 13 molecules by carbene-induced hydrogen abstraction.

The N-Heterocyclic Carbene (NHC) alane and gallane adducts (NHC)·Cp*AlH2 (NHC = Me2ImMe5, iPr2ImMe6, Dipp2Im 7) and (NHC)·Cp*GaH2 (NHC = Me2ImMe8, iPr2ImMe9, Dipp2Im 10; R2Im = 1,3-di-organyl-imidazolin-2-ylidene; Dipp = 2,6 diisopropylphenyl; Me2ImMe = 1,3,4,5-tetra-methyl-imidazolin-2-ylidene; Cp* = C5Me5) were prepared either via the reaction of (AlH2Cp*)31 with the NHC or by the treatment of (NHC)·GaH2I (NHC = Me2ImMe2, iPr2ImMe3, Dipp2Im 4) with KCp*. The reaction of (AlH2Cp*)31 with the backbone saturated NHC Dipp2ImH led to NHC ring expansion instead with the formation of (RER-Dipp2ImHH2)AlCp* 12. Heating solutions of the gallium compounds 8-10 triggered reductive elimination of Cp*H and afforded Cp*GaI16. The reaction of the alane adduct (Me2ImMe)·Cp*AlH25 with cAACMe led to the insertion of cAACMe into the Al-H bond with the formation of the compound rac-(Me2ImMe)·AlHCp*(cAACMeH) rac-14. Heating a solution of rac-14 led to irreversible isomerisation with the formation of (Me2ImMe)·AlHCp*(cAACMeH) meso-14. The alane adducts (iPr2ImMe)·Cp*AlH26 and (Dipp2Im)·Cp*AlH27 react with cAACMe with the release of the NHC and formation of the exceptionally stable oxidative addition product (cAACMeH)AlHCp* 15. Reactions of the gallane adducts 8-10 with cAACMe led to reductive elimination of cAACMe-H2 and the formation of Cp*GaI16.

Reactivity variance between stereoisomers of saturated N-heterocyclic carbenes on gold surfaces

Two stereoisomers, one C2 symmetric and one Cs symmetric, of saturated N-heterocyclic carbenes (NHCs) were placed on gold films and they demonstrate different reactivity.

Six-Membered Saturated NHC-Stabilized Borenium Cations: Isolation of a Cationic Analogue of Borinic Acid.

The reaction of six-membered saturated NHC [1,3-di(2,6-diisopropylphenyl) tetrahydropyrimidine-2-ylidene; henceforth abbreviated as 6-SIDipp] with PhBCl2 yields a Lewis base adduct, 6-SIDipp·PhBCl2 (1), which readily undergoes nucleophilic substitution reaction with AgNO3, leading to the single (2) and double (3) substitution of both chlorides with ONO2 moieties at the boron atom. The reaction of 1 with 1 equiv of AlCl3 resulted in a borenium cation of composition [6-SIDipp·B(Ph)Cl]+ (4) with AlCl4- as the counteranion. Although borenium cations with different substituents on boron have been reported, a structurally characterized phenylchloroborenium cation remains unknown. Similarly, the reaction of 1 with triflic acid provides the first representative of a new class of borenium cations bearing one hydroxyl and one phenyl group on boron (5), a cationic analogue of borinic acid.

Continuous Flow Synthesis of Sulfur‐ and Selenium−NHC Compounds (NHC=N‐Heterocyclic Carbene)

AbstractThe first continuous flow syntheses of sulfur‐ and selenium−NHC (NHC=N‐heterocyclic carbene) adducts in unprecedented short reaction times and high yields are reported. The importance of these species in coordination chemistry or as efficient tools for determining the π‐acceptor character of NHC ligands make any improvement in their synthesis a worthy goal. Thiourea derivatives bearing both saturated and unsaturated NHCs were obtained using NEt3 as a weak base (homogeneous setup) in conjunction with a bed of elemental sulfur (S8). The synthetic route proving optimal for selenoureas involves the use of a simple Se/K2CO3 heterogeneous microreactor design.

3D vs. turbostratic: controlling metal-organic framework dimensionality via N-heterocyclic carbene chemistry.

Using azolium-based ligands for the construction of metal–organic frameworks (MOFs) is a viable strategy to immobilize catalytically active N-heterocyclic carbenes (NHC) or NHC-derived species inside MOF pores. Thus, in the present work, a novel copper MOF referred to as Cu-Sp5-BF4, is constructed using an imidazolinium ligand, H2Sp5-BF4, 1,3-bis(4-carboxyphenyl)-4,5-dihydro-1H-imidazole-3-ium tetrafluoroborate. The resulting framework, which offers large pore apertures, enables the post-synthetic modification of the C2 carbon on the ligand backbone with methoxide units. A combination of X-ray diffraction (XRD), solid-state nuclear magnetic resonance (ssNMR) and electron microscopy (EM), are used to show that the post-synthetic methoxide modification alters the dimensionality of the material, forming a turbostratic phase, an event that further improves the accessibility of the NHC sites promoting a second modification step that is carried out via grafting iridium to the NHC. A combination of X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) methods are used to shed light on the iridium speciation, and the catalytic activity of the Ir–NHC containing MOF is demonstrated using a model reaction, stilbene hydrogenation.

Transition metal complexes bearing atropisomeric saturated NHC ligands.

From achiral imidazolinium salts, chiral transition metal complexes containing an N-heterocyclic carbene (NHC) ligand were prepared (metal = palladium, copper, silver, gold, rhodium). Axial chirality in these complexes results from the formation of the metal-carbene bond leading to the restriction of rotation of dissymmetric N-aryl substituents about the C-N bond. When these complexes exhibited a sufficient configurational stability, a resolution by chiral high-performance liquid chromatography (HPLC) on preparative scale enabled isolation of enantiomers with excellent enantiopurities (>99% ee) and good yields. A study of the enantiomerization barriers revealed the effect of the backbone nature as well as the type of transition metal on its values. Nevertheless, the evaluation of palladium-based complexes in asymmetric intramolecular α-arylation of amides demonstrated that the ability to induce an enantioselectivity cannot be correlated to the configurational stability of the precatalysts.

Energy Decomposition Analysis Coupled with Natural Orbitals for Chemical Valence and Nucleus-Independent Chemical Shift Analysis of Bonding, Stability, and Aromaticity of Functionalized Fulvenes: A Bonding Insight.

The Donor base ligand-stabilized cyclopentadienyl-carbene compounds L–C5H4 (L = H2C, aAAC; (CO2Me)2C, Py; aNHC, NHC, PPh3; SNHC; aAAC = acyclic alkyl(amino) carbene, aNHC = acyclic N-hetero cyclic carbene, NHC = cyclic N-hetero cyclic carbene, SNHC = saturated N-hetero cyclic carbene, Py = pyridine) (1a-1d, 2a-2c, 3) have been theoretically investigated by energy decomposition analysis coupled with natural orbitals for chemical valence calculation. Among all these compounds, aNHC=C5H4 (2a) and Ph3P=C5H4 (2c) had been reported five decades ago. The bonding analysis of compounds with the general formula L=C5H4 (1a-1d) [L = (H2C, aAAC, (CO2Me)2C, Py] showed that they possess one electron-sharing σ bond and electron-sharing π bond between L and C5H4 neutral fragments in their triplet states as expected. Interestingly, the bonding scenarios have completely changed for L = aNHC, NHC, PPh3, SNHC. The aNHC analogue (2a) prefers to form one electron-sharing σ bond (CL–CC5H4) and dative π bond (CL ← CC5H4) between cationic (aNHC)+ and anionic C5H4– fragments in their doublet states. Similar bonding scenarios have been observed for NHC (2b) and PPh3 (2c) (PL–CC5H4, PL ← CC5H4) analogues. In contrast, the SNHC and C5H4 neutral fragments of SNHC=C5H4 (3) prefer to form a dative σ bond (CSNHC → CC5H4) and a dative π bond (CSNHC ← CC5H4) in their singlet states. The pyridine analogue 1d is quite different from 2c from the bonding and aromaticity point of view. The nucleus-independent chemical shifts of all the abovementioned species (1–3) corresponding to aromaticity have been computed using the gauge-independent atomic orbital approach.

A lead(II) toluene complex

A well-defined intermolecular toluene complex of lead(II) supported by a pincer-type saNHC (saturated N-heterocyclic carbene) ligand was prepared through deprotonation of the bis(imidazolinium) salt with Pb[N(SiMe3)2]2 or metalation of the free carbene and subsequent salt metathesis with Tl(OTf), followed by crystallization from toluene. Combined computational and experimental results indicate that noncovalent interactions with the lead atom (σ-sss-hole type interaction, dispersion) and the diisopropylphenyl side groups of the ligand (dispersion) stabilize the complex.

NHC-Stabilized 1,2-Dihalodiborenes: Synthesis, Characterization, and Reactivity Toward Elemental Chalcogens.

The 2-fold reduction of B2X4(NHC)2 (X = Cl, Br, I; NHC = (un)saturated N-heterocyclic carbene) yields the corresponding green-colored 1,2-dihalodiborenes B2X2(NHC)2, the 11B NMR resonances of which are strongly upfield-shifted upon descending the halide group. The diborenes crystallize as the trans isomers, with relatively short B═B double bonds (1.513(9) to 1.568(4) Å). Cyclic voltammetric experiments with these diborenes reveal reversible one-electron oxidation processes to the corresponding diboron radical cation (E1/2 = -1.16 to -1.50 V); the reducing power of B2X2(NHC)2 increasing with the electronegativity of the halide and for the less π-accepting unsaturated NHCs. The main UV-vis absorption (393-463 nm), which corresponds mainly to a highest occupied molecular orbital (HOMO) → lowest unoccupied molecular orbital (LUMO) transition, undergoes a blueshift upon descending the halide group and shows some dependence on the stereoelectronics of the NHC ligands. Computational analyses show that the HOMO of B2X2(NHC)2 is mostly localized on the B═B π bond, with the contribution from halide p orbitals decreasing down the group, and the saturated NHCs affording some π-bonding delocalization over the B-CNHC bonds. The calculated HOMO and LUMO energies decrease upon descending the halide group, while the HOMO-LUMO gap also decreases, correlating well with the cyclovoltammetry and UV-vis data. The reactions of B2Br2(NHC)2 with elemental sulfur and red selenium lead to the formation of the corresponding diborathiiranes and seleniranes, respectively, which were characterized by NMR and UV-vis spectroscopy, cyclic voltammetry, and X-ray diffraction analyses. In one case, an additional one-electron oxidation yields a unique cyclic B2Se radical cation. Computational analyses show that the localization of the HOMO and HOMO - 1 of the diboraseleniranes is inverted compared to the diborathiiranes.

Imidazolinium N-Heterocyclic Carbene Ligands for Enhanced Stability on Gold Surfaces

N-heterocyclic carbenes (NHCs) have emerged as versatile and robust ligands for noble metal surface modifications due to their ability to form compact, self-assembled monolayers. Despite a growing body of research, previous NHC surface modification schemes have employed just two structural motifs: the benzimidazolium NHC and the imidazolium NHC. However, different NHC moieties, including saturated NHCs, are often more effective in homogenous catalysis chemistry than these aforementioned motifs and may impart numerous advantages to NHC surfaces, such as increased stability and access to chiral groups. This work explores the preparation and stability of NHC-coated gold surfaces using imidazolium and imidazolinium NHC ligands. X-ray photoelectron spectroscopy and surface-enhanced Raman spectroscopy demonstrate the attachment of NHC ligands to the gold surface and show enhanced stability of imidazolinium compared to the traditional imidazolium under harsh acidic conditions.

Bis(phenolate)-functionalized N-heterocyclic carbene complexes of oxo- and imido-vanadium(V)

Oxo- and imido-vanadium(V) metal complexes supported by bis(phenolate)-functionalized N-heterocyclic carbene (NHC) ligands were synthesized and structurally identified. In the presence of [(Ph3P)2N]Cl ([PPN]Cl), saturated NHC oxo-vanadium complexes showed activity in the coupling of CO2 and cyclohexene oxide (CHO) into cis-cyclohexene carbonate (cis-CHC). More importantly, the oxo-vanadium complex bearing the less electron-donating benzannulated NHC ligand was found to be more active in CHO conversion to poly(cyclohexene carbonate) (PCHC) in addition to the cis-CHC, highlighting the beneficial effect of the weak electron-donating ability of the latter vs. saturated NHC ligands within such vanadium catalysts. Evaluation of the saturated NHC imido-vanadium catalyst performance led to the same activity and selectivity as the analogous oxo-vanadium catalysts owing to its reactivity with CO2 via a [2 + 2] cycloaddition reaction forming an oxo-vanadium species.

Stepwise Nucleophilic Substitution to Access Saturated N-heterocyclic Carbene Haloboranes with Boron–Methyl Bonds

Compounds of boranes with N-heterocyclic carbenes are known, yet little attention has been paid to NHC compounds of boron bearing methyl and halogen moieties together. The reason can be attributed ...

Unsaturated and Benzannulated N-Heterocyclic Carbene Complexes of Titanium and Hafnium: Impact on Catalysts Structure and Performance in Copolymerization of Cyclohexene Oxide with CO2.

Tridentate, bis-phenolate N-heterocyclic carbenes (NHCs) are among the ligands giving the most selective and active group 4-based catalysts for the copolymerization of cyclohexene oxide (CHO) with CO2. In particular, ligands based on imidazolidin-2-ylidene (saturated NHC) moieties have given catalysts which exclusively form polycarbonate in moderate-to-high yields even under low CO2 pressure and at low copolymerization temperatures. Here, to evaluate the influence of the NHC moiety on the molecular structure of the catalyst and its performance in copolymerization, we extend this chemistry by synthesizing and characterizing titanium complexes bearing tridentate bis-phenolate imidazol-2-ylidene (unsaturated NHC) and benzimidazol-2-ylidene (benzannulated NHC) ligands. The electronic properties of the ligands and the nature of their bonds to titanium are studied using density functional theory (DFT) and natural bond orbital (NBO) analysis. The metal–NHC bond distances and bond strengths are governed by ligand-to-metal σ- and π-donation, whereas back-donation directly from the metal to the NHC ligand seems to be less important. The NHC π-acceptor orbitals are still involved in bonding, as they interact with THF and isopropoxide oxygen lone-pair donor orbitals. The new complexes are, when combined with [PPN]Cl co-catalyst, selective in polycarbonate formation. The highest activity, albeit lower than that of the previously reported Ti catalysts based on saturated NHC, was obtained with the benzannulated NHC-Ti catalyst. Attempts to synthesize unsaturated and benzannulated NHC analogues based on Hf invariably led, as in earlier work with Zr, to a mixture of products that include zwitterionic and homoleptic complexes. However, the benzannulated NHC-Hf complexes were obtained as the major products, allowing for isolation. Although these complexes selectively form polycarbonate, their catalytic performance is inferior to that of analogues based on saturated NHC.

Synthesis of fused B,N-heterocycles by alkyne cleavage, NHC ring-expansion and C-H activation at a diboryne.

The addition of alkynes to a saturated N-heterocyclic carbene (NHC)-supported diboryne results in spontaneous cycloaddition, with complete B[triple bond, length as m-dash]B and C[triple bond, length as m-dash]C triple bond cleavage, NHC ring-expansion and activation of a variety of C-H bonds, leading to the formation of complex mixtures of fused B,N-heterocycles.

Synthesis and Reactivity of Methylpalladium Complexes Bearing a Partially Saturated IzQO Ligand

A saturated N-heterocyclic carbene–phenolate bidentate ligand, 3,3a,4,5-tetrahydroimidazo[1,5-a]quinolin-9-olate-1-ylidene (SIzQO), was synthesized and characterized. The SIzQO ligand was then treated with PdClMe(pyridine)2 and [Pd(μ-Cl)Me(2,6-lutidine)]2, which afforded C,C-cis-(SIzQO)PdMe(pyridine) and the thermodynamically unstable trans isomer C,C-trans-(SIzQO)PdMe(2,6-lutidine), respectively. The latter isomerizes at 40 °C into the corresponding cis isomer via a dissociative mechanism. These palladium/SIzQO complexes catalyze the polymerization of ethylene at 100–120 °C, although the catalytic activity is lower than that of a previously reported palladium/imidazo[1,5-a]quinolin-9-olate-1-ylidene (IzQO) system.

Azoliniums, Adducts, NHCs and Azomethine Ylides: Divergence in Wanzlick Equilibrium and Olefin Metathesis Catalyst Formation.

The dimerization of a saturated N-heterocyclic carbene (NHC) to tricyclic piperazine in preference to the commonly observed Wanzlick dimerization is presented. Mechanistic investigations revealed that the N-fluorene substituent of the heterocycle is implicated in both ring opening of corresponding carbene dimer and tautomerization of NHC to an azomethine ylide. This has consequences for the fate of the NHC when generated from either an azolinium salt or a pentafluorophenyl adduct. The insights gained permitted the synthesis of a new indenylidene metathesis precatalyst, which exhibits exceptional selectivity and high TONS in self-metathesis of 1-octene.

2,6-Lutidine-linked bis-saturated NHC pincer ligands, silver complexes and transmetallation

Pincer ligands have proven to be valuable tools in the formation of robust transition metal complexes. To date, pincer ligands have featured an extremely diverse array of structural motifs, backbones and donor units. Carbene ligands have been easily integrated into a variety of pincer ligand structures and yet there are very few examples in which saturated NHC donor moieties are featured. Saturated NHCs are known to have unique donor and acceptor properties compared to their unsaturated analogs and therefore their implementation into pincer structures should lead to new electronic properties of the coordinated metal. To expand the use of saturated NHCs in pincer ligand chemistry, a bis-NHC pincer ligand, featuring a 2,6-lutidine linker, has been synthesized. The proligand can be directly metalated using silver oxide and the silver salt has been used in transmetallation chemistry to generate Ni(II) pincer complexes. This ligand is an excellent addition to known pincer ligands and will have applications in catalysis and other areas.

Front Cover Picture: A Structure‐Based Activity Study of Highly Active Unsymmetrically Substituted NHC Gold(I) Catalysts (Adv. Synth. Catal. 1/2018)

The front cover image, provided by Stephen Hashmi and co-workers, illustrates the results of their work on the synthesis and catalytic activity of saturated and unsaturated NHC as well as NHOC gold(I) complexes. The catalytic activity is strongly influenced by the type of ligand and by side-chain ring size. For the furane-yne cyclization the saturated NHC bearing a 15-membered ring as a side-chain is the match winner, as indicated by the position on the winners’ rostrum. The cover artist is Jasmin Schießl. Details of this work can be found in the full paper on pages 106–111 (P. Zargaran, T. Wurm, D. Zahner, J. Schießl, M. Rudolph, F. Rominger, A. S. K. Hashmi, Adv. Synth. Catal. 2018, 360, 106–111; DOI: 10.1002/adsc.201701080).

A Structure‐Based Activity Study of Highly Active Unsymmetrically Substituted NHC Gold(I) Catalysts

AbstractFollowing the modular template synthesis using isonitriles, new unsymmetrically substituted five‐membered saturated N‐heterocyclic carbene (NHC) and N‐heterocyclic oxo‐carbene (NHOC) gold(I) complexes were prepared. With these species and already reported complexes, a detailed study concerning the catalytic activities of the complex classes available by the isonitrile route was conducted. The catalytic properties of twelve different types of NHOCs, saturated and unsaturated NHC gold(I) pre‐catalysts with different substituents, as well as one representative of a six‐membered NHC and one N‐acyclic carbene (NAC) gold(I) complex were analyzed by utilizing the phenol synthesis as a test reaction. For this reaction, the saturated NHC gold(I) complexes achieved higher conversions than the corresponding unsaturated NHCs and the NHOC systems. While unsaturated NHC complexes show higher catalytic activity during the initial phase of the conversion, due to a higher stability, higher turnover numbers (TONs) were obtained for the corresponding saturated systems. A cyclopentadecyl substituent at nitrogen turned out to be the privileged substituent for all of the unsymmetrical complexes. Furthermore, we detected that light exclusion can significantly increase the catalytic activity of NHC gold(I) complexes for phenol synthesis.magnified image

C−N Bond Activation and Ring Opening of a Saturated N‐Heterocyclic Carbene by Lateral Alkali‐Metal‐Mediated Metalation

AbstractCombining alkali‐metal‐mediated metalation (AMMM) and N‐heterocyclic carbene (NHC) chemistry, a novel C−N bond activation and ring‐opening process is described for these increasingly important NHC molecules, which are generally considered robust ancillary ligands. Here, mechanistic investigations on reactions of saturated NHC SIMes (SIMes=[:C{N(2,4,6‐Me3C6H2)CH2}2]) with Group 1 alkyl bases suggest this destructive process is triggered by lateral metalation of the carbene. Exploiting co‐complexation and trans‐metal‐trapping strategies with lower polarity organometallic reagents (Mg(CH2SiMe3)2 and Al(TMP)iBu2), key intermediates in this process have been isolated and structurally defined.