RESUMO
NHC-phosphinidene (NHCP) adducts are an emerging class of ligands with proven binding ability for main group and transition metal elements. They possess electron-rich P atoms with two lone pairs (LPs) of electrons, making them interesting platforms for the formation of multimetallic complexes. We describe herein a modular, high-yielding synthesis of bis(NHCP)s, starting from alkylidene-bridged bis(NHC)s ((IMe)2CnH2n; n = 1,3) and triphosphirane (PDip)3 (Dip = 2,6-iPr2C6H3) as phosphinidene transfer reagent. The coordination chemistry of [{DipP(IMe)}2CH2], 1, was studied in detail, and complexes [1·FeBr2] and [1·Rh(cod)]Cl were prepared, showing that the ligand has a flexible bite angle. The dicarbonyl complex [1·Rh(CO)2]Cl, with an average value for the CO stretching frequency of 2029 cm-1, indicates a strongly donating ligand when compared to related complexes. The binding ability of the remaining two phosphorus LPs was demonstrated with AuCl(SMe2), giving the heterotrimetallic complex [1·(AuCl)2·Rh(cod)]Cl. Moreover, [1·Rh(cod)]X (X- = Cl, B(3,5-(CF3)2-C6H3)4) was tested in the catalytic hydrogenation of methyl-Z-α-acetamidocinnamate (MAC) and dimethyl itaconate (ItMe2), revealing that the chloride complex was inactive, while the BArF complex demonstrated moderate activity. Additionally, [1·Rh(cod)]Cl was shown to be moderately air- and moisture-stable, slowly decomposing to the corresponding NHC-stabilized bis-dioxophosphorane, which was independently synthesized by treating the free ligand with dry O2.
RESUMO
Dedicated to Professor Manfred Scheer on the occasion of his 65th birthday The reaction of (1)Ni(η2 -cod), 2, incorporating a chelating bis(N-heterocyclic carbene) 1, with P4 in pentane yielded the dinuclear complex [(2)Ni]2 (µ2 ,η2 : η2 -P4 ), 3, formally featuring a cyclobutadiene-like, neutral, rectangular, π-bridging P4 -ring. In toluene, the butterfly-shaped complex [(1)Ni]2 (µ2 ,η2 : η2 -P2 ), 4, with a formally neutral P2 -unit was obtained from 2 and either P4 or 3. Computational studies showed that a haptotropic rearrangement involving two isomers of the µ2 ,η2 : η2 -P4 coordination mode and a low-energy µ2 ,η4 : η4 -P4 coordination mode, as previously predicted for related nickel cyclobutadiene complexes, could explain the coalescence observed in the low-temperature NMR spectra of 3. The insertion of the (1)Ni fragment into a P-P bond of P7 (SiMe3 )3 , forming complex 5 with a norbornane-like P7 ligand, was also observed.
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A nickel complex incorporating an N2 O ligand with a rare η2 -N,N'-coordination mode was isolated and characterized by X-ray crystallography, as well as by IR and solid-state NMR spectroscopy augmented by 15 N-labeling experiments. The isoelectronic nickel CO2 complex reported for comparison features a very similar solid-state structure. Computational studies revealed that η2 -N2 O binds to nickel slightly stronger than η2 -CO2 in this case, and comparably to or slightly stronger than η2 -CO2 to transition metals in general. Comparable transition-state energies for the formation of isomeric η2 -N,N'- and η2 -N,O-complexes, and a negligible activation barrier for the decomposition of the latter likely account for the limited stability of the N2 O complex.
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Flexible, chelating bis(NHC) ligand 2, able to accommodate both cis- and trans-coordination modes, was used to synthesize (2)Ni(η2 -cod), 3. In reaction with GeCl2 , it produced (2)NiGeCl2 , 4, featuring a T-shaped Ni0 and a pyramidal Ge center. Complex 4 could also be prepared from [(2)GeCl]Cl, 5, and Ni(cod)2 , in a reaction that formally involved Ni-Ge transmetalation, followed by coordination of the extruded GeCl2 moiety to Ni. A computational analysis showed that 4 possesses considerable multiconfigurational character and the NiâGe bond is formed through σ-donation from the Ni 4s, 4p, and 3d orbitals to Ge. (NHC)2 Ni(cod) complexes 9 and 10, as well as (NHC)2 GeCl2 derivative 11, incorporating ligands that cannot accommodate a wide bite angle, failed to produce isolable Ni-Ge complexes. The isolation of (2)Ni(η2 -Py), 12, provides further evidence for the reluctance of the (2)Ni0 fragment to act as a σ-Lewis acid.
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A Ni(0)-NCN pincer complex featuring a six-membered N-heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its Ni(II) precursor. It retained chloride in the square-planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni(0) 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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Chelating ligands have had a tremendous impact in coordination chemistry and catalysis. Notwithstanding their success as strongly σ-donating and π-accepting ligands, to date no chelating bis[cyclic (alkyl)(amino)carbenes] have been reported. Herein, we describe a chelating, C2-symmetric bis[cyclic (alkyl)(amino)carbene] ligand, which was isolated as a racemic mixture. The isolation and structural characterization of its isostructural, pseudotetrahedral complexes with iron, cobalt, nickel, and zinc dihalides featuring eight-membered metallacycles demonstrates the binding ability of the bis(carbene). Reduction of the nickel(II) dibromide with potassium graphite produces a dicoordinate nickel(0) complex that features one of the narrowest angles measured in any unsupported dicoordinate transition metal complexes.
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Isomeric bis(aldiminium) salts with a 1,4-cyclohexylene framework were synthesized. The first isolable bis(CAAC) was prepared from the trans-stereoisomer and its ditopic ligand competency was proven by conversion to iridium(I) and rhodium(I) complexes. Upon deprotonation, the cis-isomer yielded an electron rich olefin via a classic, proton-catalyzed pathway. The CîC bond formation from the desired cis-bis(CAAC) was shown to be thermodynamically very favorable and to involve a small activation barrier. Compounds that can be described as insertion products of the cis-bis(CAAC) into the E-H bonds of NH3, CH3CN and H2O were also identified.
Assuntos
Metano , Ródio , Alcenos/química , Ligantes , Metano/análogos & derivados , Metano/químicaRESUMO
A series of rhodium complexes, [Rh(cod)(NHC-F(x))(OH(2))] (cod = 1,5-cyclooctadiene; NHC = N-heterocyclic carbene), incorporating anionic N-heterocyclic carbenes with 2-tert-butylmalonyl backbones and 2,6-dimethylphenyl (x = 0), 2,6-difluorophenyl (x = 4), 2,4,6-trifluorophenyl (x = 6), and pentafluorophenyl (x = 10) N,N'-substituents, respectively, has been prepared by deprotonation of the corresponding zwitterionic precursors with potassium hexamethyldisilazide, followed by immediate reaction of the resulting potassium salts with [{RhCl(cod)}(2)]. These complexes could be converted to the related carbonyl derivatives [Rh(CO)(2)(NHC-F(x))(OH(2))] by displacement of the COD ligand with CO. IR and NMR spectroscopy demonstrated that the degree of fluorination of the N-aryl substituents has a considerable influence on the σ-donating and π-accepting properties of the carbene ligands and could be effectively used to tune the electronic properties of the metal center. The carbonyl groups on the carbene ligand backbone provided a particularly sensitive probe for the assessment of the metal-to-ligand π donation. The ortho-fluorine substituents on the N-aryl groups in the carbene ligands interacted with the other ligands on rhodium, determining the conformation of the complexes and creating a pocket suitable for the coordination of water to the metal center. Computational studies were used to explain the influence of the fluorinated N-substituents on the electronic properties of the ligand and evaluate the relative contribution of the σ- and π-interactions to the ligand-metal interaction.
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A series of 1,3-bis(2,6-diisopropylphenyl)-5-methyl-1,3-diaza-4,6-diborabenzenes with methyl, phenyl, and dimethylamino substituents on the ring boron atoms were prepared using the cyclocondensation reaction between N,N'-bis(2,6-diisopropylphenyl)trimethylsilylformamidine and the appropriately substituted 1,1-bis(organochloroboryl)ethane, followed by deprotonation of the cationic ring intermediate. The planar, heterocyclic benzene analogues could be further deprotonated at the other ring carbon using an additional equivalent of potassium hexamethyldisilazide to yield organometallic derivatives akin to the potassium phenylide. The potassium cations could be efficiently sequestered in both solution and solid state using 18-crown-6, and the crystallographic analysis of the reaction products revealed the absence of carbanion-cation contacts in the solid state. The transformation of a planar, tricoordinate sp(2) carbon to a tricoordinate, contact ion-pair carbanion and further to a solvent-separated, free dicoordinate carbanion was investigated using solution NMR and single-crystal X-ray diffraction. The first isolation and characterization of free dicoordinate carbanions in the solid state is supported by a charge distribution analysis, and the relationship between phenylide-type carbanions and N-heterocyclic carbenes is discussed through the prism of the results reported herein.
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The reaction of Cp(x)(2)ZrCl(2) (Cp(x) = Cp, Cp*) with ammonia borane in presence of n-butyllithium yielded Cp(2)Zr(Cl)NH(2)BH(3) and Cp(x)(2)Zr(H)NH(2)BH(3). These derivatives are isoelectronic with the ethyl zirconocene chloride and hydride, respectively, and feature a chelating amidoborane ligand coordinating through a Zr-N bond and a Zr-H-B bridge. In solution, each of the complexes consists of an equilibrium mixture of two isomers differing in the orientation of the amidoborane ligand with respect to the Zr-X bond (X = H, Cl), while in the solid state, only one isomer was observed. Such isomers have not been characterized for any metal complexes containing the isoelectronic beta-agostic ethyl ligand or any other agostic alkyl group.
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A neutral, formally 16pi-electron, tricyclic tetrahydrazidotetraborane was obtained in a two-step procedure involving self-assembly of a dilithiodiborate with B(4)N(8) framework and subsequent oxidation of the phenylborate moieties to boranes and biphenyl using Fe(II) as an oxidant.
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A heterocyclic cyclopentadienyl analog containing only one carbon atom in the ring was prepared and a polymeric lithiocene and a monomeric zincocene containing this novel ligand have been isolated and crystallographically characterized.
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The ß-diketiminate ligand framework is shown to undergo reduction to form a neutral main group radical stabilized by spiroconjugation of the unpaired electron over the group 13 element centre. The synthesized paramagnetic complex was characterized by EPR spectroscopy and computational chemistry.
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Ruthenium and iron sandwich complexes incorporating cyclopentadienyl analogs with CB(2)N(2)(-) skeletons were characterized. Electrochemical measurements supported by computational studies revealed that in combination with larger metal ions such as Ru the CB(2)N(2)(-) ligand can be more electron-rich than its organic counterpart.
RESUMO
The electronic structures of known N-heterocyclic carbenes (NHCs) with boron, nitrogen, and phosphorus backbones are examined using quantum chemical methods and compared to the experimental results and to the computational data obtained for a classical carbon analogue, imidazol-2-ylidene. The sigma-donor and pi-acceptor abilities of the studied NHCs in selected transition-metal complexes are evaluated using a variety of approaches such as energy and charge decomposition analysis, as well as calculated acidity constants and carbonyl stretching frequencies. The study shows that the introduction of selected heteroatoms into the NHC backbone generally leads to stronger metal-carbene bonds and therefore improves the ligand properties of these systems. The backdonation of pi-electron density from the metal to the ligand is found to be strong in complexes of the studied NHCs with group 11 metals, where it constitutes up to nearly 35% of the total orbital interaction energy. The ligand properties of the aluminum analogues of some of the reported NHCs with boron backbones are also assessed.
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Two heterocyclic cyclopentadienyl analogs with a CB2N2 skeleton, 4-methyl-1,2,3,5-tetraphenyl-1,2-diaza-3,5-diborolidine and 4-methyl-3,5-dimethylamino-1,2-diphenyl-1,2-diaza-3,5-diborolidine were prepared through cyclocondensation of the corresponding 1,1-bis(organochloroboryl)ethane with 1,2-diphenylhydrazine. The former diazadiborolidine featured a cyclopentadiene-like structure with short B-N bonds and a planar ring framework, while in the latter the B-N bonds were noticeably longer and the ring framework was considerably folded as a result of the interaction between boron and the electron donating NMe2 groups. The dimethylamino substituted diazadiborolidine could not be deprotonated due to the reduced acidity of the ring proton, however, the B-phenylated analog was easily deprotonated and the lithium, sodium and potassium 1,2-diaza-3,5-diborolyls were isolated and structurally characterized. The solid state structures of the lithium and sodium salts were similar, with an eta(1)-coordinated pi ligand and three THF molecules completing the coordination sphere of the metal. The potassium salt featured a highly unusual mono-dimensional polymeric structure with the metal pi-coordinated by the CB2N2 ligand and two of the phenyl groups on boron and nitrogen, and sigma-coordinated by one THF molecule.
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Lithium (2a), sodium (2b), and potassium (2c) salts of 1-methyl-3,5-diphenyl-4-methylamino-1,2,4-triaza-3,5-diborolyl were prepared by deprotonation of the ring nitrogen in neutral precursor 1. The alkali metal derivatives were characterized by multinuclear NMR, mass spectrometry, and single-crystal X-ray diffraction. The structural determinations revealed extended 2D structures for 2a and 2b and an extended 1D structure for 2c. All three solvent-free structures are dominated by sigma interactions, and pi interactions are also present for the potassium derivative. Addition of triphenylborane to 2a, 2b, and 2c produced the adducts 3a, 3b, and 3c, respectively, and these were characterized by multinuclear NMR and mass spectrometry. Structural determinations have been performed for the lithium and potassium salt, showing that Ph3B coordinates at the 2 position of the ring, whereas the alkali metal is coordinated by the pendant methylamino group. The lithium ion is additionally coordinated by three acetonitrile molecules in the monomeric structure of 3a, whereas the potassium ion is coordinated by three phenyl groups, forming the 1D polymeric structure of 3c. Reaction of 2a with [Rh(cod)Cl]2 yielded the dimeric 4, containing two 1,2,4-triaza-3,5-diborolyl rings bridging two Rh(cod) fragments through the substituent-free ring nitrogen atoms.
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The electronic structures of 15 group 13-16 carbene analogues are analyzed using various quantum chemical methods and compared to the data obtained for the parent N-heterocyclic carbene (NHC), imidazol-2-ylidene. The results of this study present a uniform analysis of the similarities and differences in the electronic structures of p-block main-group carbene analogues. Though all systems are formally isovalent, the theoretical analyses unambiguously indicate that their electronic structures run the gamut from C=C localized (group 13) to C=N localized (group 16) via intermediate, more delocalized, systems. In particular, neither the stibenium ion nor any of the chalcogenium dications is a direct analogue of imidazol-2-ylidene as they all contain two lone pairs of electrons around the divalent main-group center, instead of the expected one. The reason behind the gradual change in the electronic structure of main-group analogues of imidazol-2-ylidene was traced to the total charge of the systems, which changes from anionic to dicationic when moving from left to right in the periodic table. Results from theoretical analyses of aromaticity show that all group 13-16 analogues of imidazol-2-ylidene display some degree of aromatic character. The heavier group 13 anions benefit the least from pi-electron delocalization, whereas the cationic group 15 systems are on par with the parent carbon system and display only slightly less aromatic character than cyclopentadienide, a true 6pi-electron aromatic species. The sigma-donor and pi-acceptor ability of the different main-group carbene analogues are also evaluated.