RESUMO
Terminal imido complexes containing metal-nitrogen multiple bonds have been widely used in organometallic chemistry and homogeneous catalysis. The role of terminal imido ligands spans from reactive sites to spectator motifs, largely depending on the nature of the metal center and its specific coordination sphere. Aiming at identifying reactivity descriptors for M-N multiple bonds, we herein explore solid-state 15N NMR spectroscopy (ssNMR) on early transition metal terminal imido complexes augmented by computational studies and show that the asymmetry parameter, κ (skew, 1 ≥ κ ≥ -1), readily available from experiments or calculations, is diagnostic for the reactivity of M-N multiple bonds in imido complexes. While inert imido ligands exhibit skew values (κ) close to 1, highly reactive imido moieties display significantly lower skew values (κ ⪠1) as found in metallocene or bis-imido complexes. Natural chemical shielding analysis shows that skew values away from 1 are associated with an asymmetric development of π-orbitals around the M-N multiple bond of the imido moiety, with a larger double-bond character for reactive imido. Notably, this descriptor does not directly relate to the M-N-C bond angle, illustrating the shortcoming of evaluating bonding and hybridization from geometrical parameters alone. Overall, this descriptor enables to obtain direct experimental evidence for the π-loading effect seen in bis(imido) and related complexes, thus explaining their bonding/reactivity.
RESUMO
Olefin metathesis has become an efficient tool in synthetic organic chemistry to build carbon-carbon bonds, thanks to the development of Grubbs- and Schrock-type catalysts. Olefin coordination, a key and often rate-determining elementary step for d0 Schrock-type catalysts, has been rarely explored due to the lack of accessible relevant molecular analogues. Herein, we present a fully characterized surrogate of this key olefin-coordination intermediate, namely, a cationic d0 tungsten oxo-methylidene complex bearing two N-heterocyclic carbene ligandsâ[WO(CH2)Cl(IMes)2](OTf) (1) (IMes = 1,3-dimesitylimidazole-2-ylidene, OTf-triflate counteranion), resulting in a trigonal bipyramidal (TBP) geometry, along with its neutral octahedral analogue [WO(CH2)Cl2(IMes)2] (2)âand an isostructural oxo-methylidyne derivative [WO(CH)Cl(IMes)2] (3). The analysis of their solid-state 13C and 183W MAS NMR signatures, along with computed 17O NMR parameters, helps to correlate their electronic structures with NMR patterns and evidences the importance of the competition among the three equatorial ligands in the TBP complexes. Anchored on experimentally obtained NMR parameters for 1, computational analysis of a series of olefin coordination intermediates highlights the interplay between σ- and π-donating ligands in modulating their stability and further paralleling their reactivity. NMR spectroscopy descriptors reveal the origin for the advantage of the dissymmetry in σ-donating abilities of ancillary ligands in Schrock-type catalysts: weak σ-donors avoid the orbital-competition with the oxo ligand upon formation of a TBP olefin-coordination intermediate, while stronger σ-donors compromise M≡O triple bonding and thus render olefin coordination step energy demanding.
RESUMO
Low-valent tungsten species generated from WCl6 and N,N'-bis(trimethylsilyl)-2,5-dimethyldihydropyrazine (Si-Me2-DHP) promotes the catalytic formation of N-phenyl-2,3,4,5-tetraarylpyrroles 3aa-ka from diarylacetylenes 1a-k and azobenzene (2a). An initial catalyst activation process is a three-electron reduction of WCl6 with Si-Me2-DHP to afford transient 'WCl3' species. Catalytically active bis(imido)tungsten(VI) species via successive one-electron reduction and NâN bond cleavage of 2a was revealed by isolating W(âNPh)2Cl2(PMe2Ph)2 from imidotungsten(V) trichloride and 2a in the presence of PMe2Ph. The superior catalytic activity of the tungsten catalyst was clarified by a density functional theory study: activation energies for the key three steps, [2 + 2]-cycloaddition of WâNPh and diarylacetylene to form (iminoalkylidene)tungsten species, enyne metathesis with second diarylacetylene, and C-N bond formation, are reasonable values for the catalytic reaction at 180 °C. In addition, this tungsten catalyst overcame two distinct deactivation processes: α-enediamido formation and aggregation of the low-valent species, both of which were observed for previously developed vanadium and titanium catalysts. We also demonstrated the synthetic utility of pentaarylpyrroles 3aa and 3ba as well as N-(2-bromophenyl)-2,3,4,5-tetraarylpyrrole 3ab by derivatizing their π-conjugated compounds 9aa, 10ba, and 11ab.
RESUMO
Since its emergence over 50 years ago, the structure of surface sites in Ziegler-Natta catalysts, which are responsible for a major fraction of the world's supply of polyethylene (PE) and polypropylene (PP), has remained elusive. This is in part due to the complexity of these systems that involve multiple synthetic steps and components, namely, the MgCl2 support, a transition-metal chloride, and several organic modifiers, known as donors, that are used prior and in some instances during the activation step with alkyl aluminum. Due to the favorable nuclear magnetic resonance (NMR) properties of V and its use in Ziegler-Natta catalysts, we utilize 51V solid-state NMR spectroscopy to investigate the structure of VOCl3 on MgCl2(thf)1.5. The resulting catalyst shows ethylene polymerization activity similar to that of its Ti analogues. Using carefully benchmarked density functional theory (DFT) calculations, the experimental 51V NMR signature was analyzed to elucidate the structure of the surface sites. Using this approach, we demonstrate that the 51V NMR signature contains information about the coordination environment, i.e., the type of ancillary ligand, and the morphology of the MgCl2 support. Analysis of the NMR signature shows that the adsorption of VOCl3 on MgCl2(thf)1.5 generates a well-defined hexacoordinated V-oxo species containing one alkoxy and four chloride ligands, whose local geometry results from the interaction with an amorphous MgCl2 surface. This study illustrates how NMR spectroscopy, which is highly sensitive to the local environment of the investigated nuclei, here V, enables us to identify the exact coordination sphere and to address the effect of the support morphology on surface site structures.
RESUMO
Imido complexes of early transition metals are key intermediates in the synthesis of many nitrogen-containing organic compounds. The metal-nitrogen double bond of the imido moiety undergoes [2+2] cycloaddition reactions with various unsaturated organic molecules to form new nitrogen-carbon and nitrogen-heteroatom bonds. This review article focuses on reactivity of the terminal imido complexes of Group 4-6 metals, summarizing their stoichiometric reactions and catalytic applications for a variety of reactions including alkyne hydroamination, alkyne carboamination, pyrrole formation, imine metathesis, and condensation reactions of carbonyl compounds with isocyanates.
RESUMO
The combination of VCl3(THF)3 and N, N-bis(trimethylsilyl)aniline (1a) is an efficient catalyst for the [2+2+1] coupling reaction of alkynes and azobenzenes, giving multisubstituted pyrroles. A plausible reaction mechanism involves the generation of a mono(imido)vanadium(III) species as an initiation step, where 1a served as an imido source with concomitant release of 2 equiv of ClSiMe3, followed by a reaction with azobenzene to form a catalytically active bis(imido)vanadium(V) species via NâN bond cleavage.
Assuntos
Alcinos/química , Compostos Azo/química , Complexos de Coordenação/química , Pirróis/síntese química , Catálise , Ciclização , Estrutura Molecular , Vanádio/químicaRESUMO
We report the syntheses of 2-pyridylimido complexes of tantalum and niobium by NâN bond cleavage of 2,2'-azopyridine. Reaction of MCl5 (M = Ta and Nb) with 2,2'-azopyridine in the presence of 0.5 equiv of 1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene (abbreviated Si-Me-CHD) afforded a dark red solution (for Ta) and a dark blue solution (for Nb) with some insoluble precipitates. After removing the solids, another 0.5 equiv of Si-Me-CHD was added to each solution, giving [M(âNpy)Cl3]n (1a: M = Ta; 1b: M = Nb) through reductive cleavage of the NâN bond of 2,2'-azopyridine. The initial products of the above reactions were determined to be 2,2'-azopyridine-bridged dinuclear complexes, [(MCl4)2(µ-pyNNpy)] (2a: M = Ta; 2b: M = Nb), which were isolated by treating MCl5 with 2,2'-azopyridine and Si-Me-CHD in a 2:1:1 molar ratio. In 2a and 2b, the NâN bond was reduced to a single bond via two-electron reduction. Further reduction of complexes 2a and 2b with 1 equiv of Si-Me-CHD afforded complexes 1a and 1b. An anionic doubly µ-imido-bridged ditantalum complex, [nBu4N][Ta2(µ-Npy)2Cl7] (3a), was generated upon addition of nBu4NCl to complex 1a, while addition of nBu4NCl to niobium complex 1b gave a polymeric terminal imido complex, [nBu4N]n/2[{Nb(âNpy)Cl3}2(µ-Cl)]n/2 (3b). Complexations of 1a and 1b with 1 equiv of 2,2'-bipyridine resulted in the formation of mononuclear 2-pyridylimido complexes, M(âNpy)Cl3(bipy) (4a: M = Ta; 4b: M = Nb), whose main structural feature is intramolecular hydrogen bonding between the ortho hydrogen atom of 2,2'-bipyridine and the nitrogen atom of the pyridyl group on the imido ligand. Isolated 2-pyridylimido complexes 4a and 4b reacted with [RhCl(cod)]2 to produce the corresponding early-late heterobimetallic complexes, (bipy)MCl3(µ-Npy)RhCl(cod) (5a: M = Ta; 5b: M = Nb).
RESUMO
X-ray absorption spectroscopy (XAS) has been central to the study of the Phillips polymerization catalyst (CrO3/SiO2). As Cr K-edge XAS signatures are sensitive to the oxidation state, geometry and types of ligands on surface (active) sites, the superposition of these effects makes their interpretation challenging. Notably, CO has been particularly used as a reductant to generate low valent Cr sites from CrO3/SiO2 and as a structural IR probe for analysing reduced Cr surface sites. Hence, it is essential to establish a solid understanding of the spectroscopic impact of CO on low-valent Cr sites. We thus built a series of fully characterized low-valent Cr molecular compounds bearing isoelectronic isocyanide ligands in place of CO, with the goal of understanding the effect of the coordination of π-acceptor ligands on the XANES signature of Cr sites. Cr K-edge spectra supplemented with DFT calculations elucidate the effect of the coordination of π-acceptor ligands on XAS signatures, giving a sharp resonance at the white line while modifying the fine structure due to short Cr-C distances and stability of low-spin Cr(ii/iii) species. The isocyanide references allow the deconvolution of the XAS spectra of the reduced CrO3/SiO2 catalyst by evaluating the types of surface species and relative amounts of bound CO at different CO pressures and temperatures.
RESUMO
Treatment of Ziegler-Natta (ZN) catalysts with BCl3 improves their activity by increasing the number of active sites. Here we show how 47/49Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of the Ti surface sites present in such treated ZN pre-catalysts, prior to activation with alkyl aluminum. High-field (21.1 T) and low-temperature (â¼100 K) NMR augmented by DFT modeling on the pre-catalyst and corresponding molecular analogues enables the detection of 47/49Ti NMR signatures and a molecular level understanding of the electronic structure of Ti surface sites. The associated Ti surface sites exhibit 49Ti NMR signatures (δiso, exp = -170 ppm; CQ, exp = 9.3 MHz; κ = 0.05) corresponding to well-defined fully chlorinated hexacoordinated Ti sites adsorbed on a distorted surface of the MgCl2 support, formed upon post-treatment with BCl3 and removal of the alkoxo ligands, paralleling the increased polymerization activity.
RESUMO
The Union Carbide (UC) ethylene polymerization catalysts, based on chromocene dispersed on silica, show distinct features from the Phillips catalysts, but share the same heated debate regarding the structure of their active sites. Based on a combination of IR, EPR spectroscopies, labeling experiments, and DFT modeling, we identified monomeric surface-supported Cr(iii) hydrides, ([triple bond, length as m-dash]SiO)Cr(Cp)-H, as the active sites of the UC catalyst. These sites are formed in the presence of grafted and adsorbed chromocene as well as residual surface OH groups, only possible at high Cr loading, and involve a C-H activation of the Cp ring. These Cr-hydrides initiate polymerization, yielding Cr(iii) alkyl species that insert ethylene through a Cossee-Arlman-type mechanism, as evidenced by spectroscopic studies. These insights inspired the design of a well-defined analog, CpCr(CH(SiMe3)2)2 grafted on partially dehydroxylated silica, that shows similar spectroscopic and polymer structure to the UC catalyst, further supporting the proposed active site structure.
RESUMO
Titania-supported vanadia (VO x /TiO2) catalysts exhibit outstanding catalytic in a number of selective oxidation and reduction processes. In spite of numerous investigations, the nature of redox transformations of vanadium and titanium involved in various catalytic processes remains difficult to detect and correlate to the rate of products formation. In this work, we studied the redox dynamics of active sites in a bilayered 5% V2O5/15% TiO2/SiO2 catalyst (consisting of submonolayer VO x species anchored onto a TiO x monolayer, which in turn is supported on SiO2) during the oxidative dehydrogenation of ethanol. The VO x species in 5% V2O5/15% TiO2/SiO2 show high selectivity to acetaldehyde and an ca. 40 times higher acetaldehyde formation rate in comparison to VO x species supported on SiO2 with a similar density. Operando time-resolved V and Ti K-edge X-ray absorption near-edge spectroscopy, coupled with a transient experimental strategy, quantitatively showed that the formation of acetaldehyde over 5% V2O5/15% TiO2/SiO2 is kinetically coupled to the formation of a V4+ intermediate, while the formation of V3+ is delayed and 10-70 times slower. The low-coordinated nature of various redox states of VO x species (V5+, V4+, and V3+) in the 5% V2O5/15% TiO2/SiO2 catalyst is confirmed using the extensive database of V K-edge XANES spectra of standards and specially synthesized molecular crystals. Much weaker redox activity of the Ti4+/Ti3+ couple was also detected; however, it was found to not be kinetically coupled to the rate-determining step of ethanol oxidation. Thus, the promoter effect of TiO x is rather complex. TiO x species might be involved in a fast electron transport between VO x species and might affect the electronic structure of VO x , thereby promoting their reducibility. This study demonstrates the high potential of element-specific operando X-ray absorption spectroscopy for uncovering complex catalytic mechanisms involving the redox kinetics of various metal oxides.