Imido Derivatives Research Articles

Ring Expansion Metathesis Polymerization (REMP) Initiators with an Unusual Ancillary Ligand

AbstractTethered tungsten‐alkylidenes bearing azoimido ligands (M≡Nγ‐Nβ=NαR) are synthesized, characterized, and tested as initiators for ring expansion metathesis polymerization (REMP). While these ligands are typically unstable and prone to dinitrogen loss, this work demonstrates that tethered alkylidene complexes bearing azoimido ligands are stable enough to be REMP initiators. Moreover, they are more efficient, long‐lived, and stereoselective than their corresponding imido derivatives (M≡NR). Density Functional Theory (DFT) analysis of the azoimido complexes provides insight into their unusual stability.

Molybdenum-Mediated N2 -Splitting and Functionalization in the Presence of a Coordinated Alkyne.

A new [PCCP]‐coordinated molybdenum platform comprising a coordinated alkyne was employed for the cleavage of molecular dinitrogen. The coordinated η 2‐alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N2‐complex, which is converted to a dinuclear μ‐(η 1:η 1)‐N2‐bridged intermediate prior to N−N bond cleavage. Protonation, alkylation and acylation of the resulting molybdenum nitrido complex led to the corresponding N‐functionalized imido complexes. Upon oxidation of the N‐acylated imido derivative in MeCN, a fumaronitrile fragment was built up via C−C coupling of MeCN to afford a dinuclear molybdenum complex. The key finding that the strong N≡N bond may be cleaved in the presence of a weaker, but spatially constrained C≡C bond contradicts the widespread paradigm that coordinated alkynes are in general more reactive than gaseous N2.

Prediction of NLO response of substituted organoimido hexamolybedate: First theoretical framework based on p-anisidine adduct [Mo6O18(p-MeOC6H4N)]2-

The second-order nonlinear optical (NLO) responses and dipole polarizabilities of p-anisidine adduct (imido derivative of hexamolybdates/polyoxometalates/POMs/Cluster) are studied by means of time dependent density functional (TDDFT) calculations. A substantial molecular second-order NLO response has been noticed in these organic-inorganic hybrid compounds, particularly [Mo6O17 cis-(p-MeOC6H4N)2]2− (system 2) and [Mo6O18 p-MeOC6H4N]2- (system 1) having static second-order polarizability (βvec) calculated to be 1949.60 au and 1565.10 au respectively. Both p-anisidine and cis-(p-anisidine) are found to be preferred choice over the trans-(p-anisidine) adduct. There is a fair probability for these systems to be selected as efficient second-order nonlinear optical materials. The movement of charge transfer from p-anisidine to hexamolybdate cluster (D–A) along the y-axis suggests molybdenum cluster acts as an acceptor (A) whereas p-anisidine working as a donor (D) in all the studied systems which is responsible for NLO response in such adducts. An incremental increase in the computed βvec values were evaluated by incorporation of an electron donor (Metalloporphyrin) instead of p-anisidine. Furthermore, substitution of Fe over Zn in Metalloporphyrin cage has enhanced the optical nonlinearity. This research effort offers a significant understanding into metal (Fe/Zn) to metal (Mo) charge transfer through imido-linkage in hexamolybdates, which has been found to be an efficient mode to enhance NLO response as a prime example in modulation of optoelectronics.

Thorium-nitrogen multiple bonds provide evidence for pushing-from-below for early actinides

Although the chemistry of uranium-ligand multiple bonding is burgeoning, analogous complexes involving other actinides such as thorium remain rare and there are not yet any terminal thorium nitrides outside of cryogenic matrix isolation conditions. Here, we report evidence that reduction of a thorium-azide produces a transient Th≡N triple bond, but this activates C-H bonds to produce isolable parent imido derivatives or it can be trapped in an N-heterocycle amine. Computational studies on these thorium-nitrogen multiple bonds consistently evidences a σ > π energy ordering. This suggests pushing-from-below for thorium, where 6p-orbitals principally interact with filled f-orbitals raising the σ-bond energy. Previously this was dismissed for thorium, being the preserve of uranium-nitrides or the uranyl dication. Recognising that pushing-from-below perhaps occurs with thorium as well as uranium, and with imido ligands as well as nitrides, suggests this phenomenon may be more widespread than previously thought.

An Effective Route to Dinuclear Niobium and Tantalum Imido Complexes.

Thermal treatment of the trichloro complexes [MCl3(NR)py2] (R = tBu, Xyl; M = Nb, Ta) (Xyl = 2,6-Me2C6H3) under vacuum affords the dinuclear imido species [MCl2(μ-Cl)(NR)py]2 (R = tBu, Xyl; M = Nb 1, 3; Ta 2, 4) with loss of pyridine. Complexes 1-4 can be easily transformed to the mononuclear starting materials [MCl3(NR)py2] (R = tBu, Xyl; M = Nb, Ta) upon reaction with pyridine. While reactions of compounds 1 and 2 with a series of alkylating reagents render the mononuclear peralkylated imido complexes [MR3(NtBu)] (R = Me, CH2Ph, CH2CMe3, CH2CMePh, CH2SiMe3), the analogous treatment with allylmagnesium chloride results in the formation of the dinuclear niobium(IV) derivative [(NtBu)(η3-C3H5)M(μ-C3H5)(μ-Cl)2M(NtBu)py2] (5). Additionally, the treatment of the starting materials 1 and 2 with the organosilicon reductant 1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene yields the pyridyl-bridged dinuclear derivatives [M2Cl2(μ-Cl)2(NtBu)2py2]2(μ-NC4H4N)2 (M = Nb 6, Ta 7). Controlled hydrolysis reaction of 1 and 2 affords the oxo chlorido-bridged products [MCl(μ-Cl)(NtBu)py]2(μ-O) (M = Nb 8, Ta 9) in a quantitative way, while the treatment of these latter with one more equivalent of pyridine led to complexes [MCl2(NtBu)py2]2(μ-O) (M = Nb 10, Ta 11). Structural study of these dinuclear imido derivatives has been also performed by X-ray crystallography.

Development of Procedures for the Manufacture of New Ashless Polymer Additives Derived From Imido Derivatives of Succinic Acid

A technological procedure has been developed for the production of succinimide additives possessing detergent dispersant and anticorrosion properties, which can be used in lubricating oils for the reduction of carbonaceous deposits on internal combustion engine parts. New alkylenimidosuccinimides derived from N,N–bis–(β–aminoethyl)piperazine and terephthalic acid production waste materials have been synthesized. Tests showed that the new additives meet the technical specifications for succinimide additives.

Suitable Approach to Prepare N‐Substituted Niobium Complexes – Study of the Factors Controlling the Process

The reactions of the chlorosilyl‐substituted cyclopentadienyl niobium compound [Nb(η5‐C5H4SiMe2Cl)Cl4] (1) with 1 equiv. of 2‐methoxyethylamine, 3‐methoxypropylamine, and allylamine in toluene specifically afford the corresponding amine adducts [Nb(η5‐C5H4SiMe2Cl){NH2(CH2)nOMe}Cl4] (n = 2, 2; 3, 3) and [Nb(η5‐C5H4SiMe2Cl)(NH2CH2CH=CH2)Cl4] (4). In contrast, a similar reaction with 1,2‐phenylenediamine proceeds with the aminolysis of a Nb–Cl bond and the formation of the amido–amine compound [Nb(η5‐C5H4SiMe2Cl)(NHC6H4‐2‐κNH2)Cl3] (5). When such reactions are performed in the presence of 2 equiv. of an additional base, they progress through the double deprotonation of the primary amine group and the formation of a single product, the structure of which depends on the coordinating ability of the pendant donor end group. Thus, two different types of derivatives are obtained, constrained‐geometry complexes such as [Nb{η5‐C5H4SiMe2‐κN(CH2)2‐κOMe}Cl3] (6) and [Nb(η5‐C5H4SiMe2‐κNC6H4‐2‐κNH2)Cl3] (7) or imido derivatives such as [Nb(η5‐C5H4SiMe2Cl){N(CH2)3OMe}Cl2] (8) and [Nb(η5‐C5H4SiMe2Cl)(NCH2CHCH2)Cl2] (9). All of the compounds have been characterized by NMR spectroscopy, and the molecular structures of 2 and 6 have been determined by X‐ray diffraction methods.

Well-Defined Molybdenum Oxo Alkyl Complex Supported on Silica by Surface Organometallic Chemistry: A Highly Active Olefin Metathesis Precatalyst.

The well-defined silica-supported molybdenum oxo alkyl species (≡SiO-)MoO(CH2tBu)3 was selectively prepared by grafting of MoO(CH2tBu)3Cl onto partially dehydroxylated silica (silica700) using the surface organometallic chemistry approach. This surface species was fully characterized by elemental analysis and DRIFT, solid-state NMR, and EXAFS spectroscopy. This new material is related to the active species of industrial supported MoO3/SiO2 olefin metathesis catalysts. It displays very high activity in propene self-metathesis at mild (turnover number = 90 000 after 25 h). Remarkably, its catalytic performance outpaces those of the parent imido derivative and its tungsten oxo analogue.

Synthesis of Polysubstituted‐1,2,4‐Triazoles

A new series of substituted 1,2,4‐triazole derivatives have been synthesized using substituted imido derivatives and isonicotinyl hydrazine (or 4‐nitrobenzoylhydrazine) as the key intermediates. These compounds include different donor or acceptor substituents on the 1,2,4‐triazole derivatives. The structures of these compounds were confirmed by FTIR, 1H‐NMR, 13C‐NMR, and elemental analysis.

Synthesis and Reactivity of a Terminal Scandium Imido Complex

Preparation of a terminal scandium imido complex, 2·DMAP, was accomplished through thermolysis of an arylamido methyl complex, 1, stabilized by a bulky β-diketiminato ligand in the presence of 4-N,N-dimethylaminopyridine (DMAP). Mechanistic studies revealed that the reaction proceeds by initial metalation of 1, followed by rapid DMAP-promoted alkane elimination to generate the scandium imido complex. Kinetic studies of the reaction between separately synthesized metalate 3 and DMAP under pseudo-first-order conditions yielded activation parameters of ΔH⧧ = 73.5(2) kJ mol–1 and ΔS⧧ = −70.4(5) J K–1 mol–1. The reaction of 2·DMAP with tert-butyl amine or phenylacetylene resulted in addition of the N–H or C–H bond across the scandium imide linkage, respectively, to furnish complexes endo-/exo-4 and endo-5. These compounds were fully characterized, including via structural analysis, providing further evidence for the terminal scandium imido derivative 2·DMAP.

Synthesis of U(iv) imidos from Tp*2U(CH2Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) by extrusion of bibenzyl

Addition of organic azides, N(3)R (R = 2,4,6-trimethylphenyl (Mes), phenyl (Ph), 1-adamantyl (Ad)), to a solution of the uranium(III) alkyl complex, Tp*(2)U(CH(2)Ph) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate) (1), results in the formation of a family of uranium(iv) imido derivatives, Tp*(2)U(NR) (2-R). Notably, these complexes were synthesized in high yields by coupling of the benzyl groups to form bibenzyl. The uranium(IV) imido derivatives, 2-Mes, 2-Ph, and 2-Ad, were all characterized by both (1)H NMR and IR spectroscopy, and 2-Mes and 2-Ad were also characterized by X-ray crystallography. In the molecular structure of 2-Mes, typical κ(3)-coordination of the Tp* ligands was observed; however in the case of 2-Ad, one pyrazole ring of a Tp* ligand has rotated away from the metal centre, forcing a κ(2)-coordination of the pyrazoles. This results in a uranium-hydrogen interaction with the Tp* B-H. Treating these imido complexes with para-tolualdehyde results in multiple bond metathesis, forming the terminal uranium(IV) oxo complex, Tp*(2)U(O), and the corresponding imine.

ChemInform Abstract: Metal‐Free Synthesis of Imido Derivatives by Direct Oxidation of α‐Amido Sulfones.

Oxidation of α-amidoaryl sulfones with m-chloroperoxybenzoic acid under mild conditions readily provides the corresponding imides in satisfactory yields. The overall process probably involves formation of an N-acyliminium ion intermediate, which by attack of the peroxyacid anion generates the final imido derivatives.

Sulfinylaminemetathesis at oxo metal species - convenient entry into imido metal chemistry

The exchange of terminal metal oxo functionalities by N-organo and N-sulfonylimido functionalities via metathesis with bent, thus very reactive sulfinyl amines R-NSO and sulfinyl sulfonylamides R-SO(2)-NSO is described. It is demonstrated that in many cases sulfinyl amine metathesis offers a more convenient entry into imido complex synthesis than the much better investigated isocyanate metathesis at oxo complexes or condensation reactions with amines and silylated amines. Improved syntheses for some known key compounds and several new complexes of the type [V(NR)Cl(3)] and [M(NR)(2)Cl(2)] (M = Cr, Mo, W) are described. Emphasis is put on the synthesis of formerly unknown base free Lewis acids with electron-withdrawing N-substituents such as haloaryl and sulfonylaryl. Surprisingly, even [CrO(2)Cl(2)] is selectively transformed by sulfinylamines into aryl imido derivatives without any reduction by sulfur dioxide. The molecular structures of novel haloaryl imido complexes [Cr(NAr)(2)Cl(2)] Ar = C(6)F(5) and 2,4,6-Cl(3)C(6)H(2) as determined by X-ray crystallography are reported.

Metal‐Free Synthesis of Imido Derivatives by Direct Oxidation of α‐Amido Sulfones

AbstractOxidation of α‐amidoaryl sulfones with m‐chloroperoxybenzoic acid under mild conditions readily provides the corresponding imides in satisfactory yields. The overall process probably involves formation of an N‐acyliminium ion intermediate, which by attack of the peroxyacid anion generates the final imido derivatives.

(dme)MCl3(NNPh2) (dme = dimethoxyethane; M = Nb, Ta): A Versatile Synthon for [Ta═NNPh2] Hydrazido(2-) Complexes

Complexes (dme)TaCl(3)(NNPh(2)) (1) and (dme)NbCl(3)(NNPh(2)) (2) (dme =1,2-dimethoxyethane) were synthesized from MCl(5) and diphenylhydrazine via a Lewis-acid assisted dehydrohalogenation reaction. Monomeric 1 has been characterized by X-ray, IR, UV-vis, (1)H NMR, and (13)C NMR spectroscopy and contains a kappa(1)-bound hydrazido(2-) moiety. Unlike the corresponding imido derivatives, 1 is dark blue because of an LMCT that has been lowered in energy as a result of an N(alpha)-N(beta) antibonding interaction that raises the highest occupied molecular orbital (HOMO). Reaction of 1 with a variety of neutral, mono- and dianionic ligands generates the corresponding ligated complexes retaining the kappa(1)-bound [Ta-NNPh(2)] moiety.

Development of the first well-defined tungsten oxo alkyl derivatives supported on silica by SOMC: towards a model of WO3/SiO2 olefin metathesis catalyst

A well-defined, silica-supported tungsten oxo alkyl species prepared by the surface organometallic chemistry approach displays high and sustained activity in propene metathesis. Remarkably, its catalytic performances outpace those of the parent imido derivative, underlining the importance of the oxo ligand in the design of robust catalysts.

N−H and N=C Bond Formation via Germanium(III) Diradicaloid Intermediates and C−S Bond Cleavage in Reactions of the Digermyne Ar′GeGeAr′ (Ar′ = C6H3-2,6-(C6H3-2,6-Pri2)2) with Azides

Reactions of the digermyne Ar'GeGeAr' (Ar' = C(6)H(3)-2,6(C(6)H(3)-2,6-Pr(i)(2))(2)) (1) with four different azides R'N(3) (R = Me(3)Sn, (n)Bu(3)Sn, PhSCH(2), or 1-adamantanyl) are described. Treatment of 1 with Me(3)SnN(3) or (n)Bu(3)SnN(3) afforded the low-valent germanium (II) parent amido derivative, Ar'Ge(mu(2)-NH(2))(2)GeAr' (3) or the high-valent germanium (IV) parent imido derivative, Ar'((n)Bu(3)Sn)Ge(mu(2)-NH)(2)Ge(Sn(n)Bu(3))Ar' (4), respectively. Addition of AdN(3) (Ad =1-admantanyl) yielded a monoimide bridged species Ar'Ge(mu(2)-NAd)GeAr' (5). The structure of 5 differs from that of the diradicaloid Ar'Ge(mu(2)-NSiMe(3))(2)GeAr' (2), which was previously obtained from the analogous reaction of 1 with Me(3)SiN(3). The reaction of 1 with PhSCH(2)N(3) afforded the germanium ketimide Ar'Ge(SPh)(2)(N=CH(2)) (6) containing the imino -N=CH(2) functional group. These reactions demonstrate a remarkable product dependence on the azide substituent. All compounds were spectroscopically and structurally characterized. Both 3 and 4 feature a four-membered Ge(2)N(2) core. The structure of 5 is stabilized by CH-pi interactions while 6 features a rare example of a pi-pi interaction between an aromatic ring and a non-aromatic double bond (N=C). The mechanism of formation of 3-6 are discussed. It is proposed that 3 and 4 are obtained via diradical imido intermediates followed by H-abstraction from solvents, whereas 6 was formed by the activation of azide group in concert with C-S bond cleavage.

Carbon Dioxide Activation with Sterically Pressured Mid- and High-Valent Uranium Complexes

Sterically pressured mid- to high-valent uranium complexes with an aryloxide substituted triazacyclononane ligand scaffold, [(((R)ArO)3tacn)(3-)], were studied for carbon dioxide activation and transformation chemistry. The high valent uranium(V) imido species [(((R)ArO)3tacn)U(NR)] (R = (t)Bu, R' = 2,4,6-trimethylphenyl (2-(t)Bu); R = Ad, R' = 2,4,6-trimethylphenyl (2-Ad); R = (t)Bu, R' = phenyl (3-(t)Bu)) were synthesized and spectroscopically characterized. X-ray crystallography of the tert-butyl mesityl imido derivative, 2-(t)Bu , reveals coordination of a bent imido fragment with a relatively long U-N bond distance of 2.05 A. The mesityl imido complexes reacted with carbon dioxide, readily extruding free isocyanate to produce uranium(V) terminal oxo species, [(((R)ArO)3tacn)U(O)] (R = (t)Bu (4-(t)Bu), Ad (4-Ad)), presumably through multiple bond metathesis via a uranium(V) carbimate intermediate. Using the smaller phenyl imido fragment in 3-(t) Bu slowed isocyanate loss, allowing the uranium(V) carbimate intermediate to undergo a second metathesis reaction, ultimately producing the diphenyl ureate derivative, [(((tBu)ArO)3tacn)U(NPh2)CO] (5-(t)Bu). Single crystal X-ray diffraction studies were carried out on both uranium(V) terminal oxo complexes and revealed short U-O bonds (1.85 A) indicative of a formal UO triple bond. The electronic structure of the oxo U(V) complexes was investigated by electronic absorption and EPR spectroscopies as well as SQUID magnetization and DFT studies, which indicated that their electronic properties are highly unusual. To obtain insight into the reactivity of CO2 with U-N bonds, the reaction of the uranium(IV) amide species, [(((R)ArO)3tacn)U(NHMes)] (R = (t)Bu (6-(t)Bu), Ad (6-Ad) with carbon dioxide was investigated. These reactions produced the uranium(IV) carbamate complexes, [(((R)ArO)3tacn)U(CO2NHMes)] (R = (t)Bu (7-(t)Bu), Ad (7-Ad)), resulting from insertion of carbon dioxide into U-N(amide) bonds. The molecular structures of the synthesized uranium carbamate complexes highlight the different reactivities due to the steric pressure introduced by the alkyl derivatized tris(aryloxide) triazacyclononane ligand. The sterically open tert-butyl derivative creates a monodentate eta(1)-O bound carbamate species, while the sterically more bulky adamantyl-substituted compound forces a bidentate kappa(2)-O,O coordination mode of the carbamate ligand.

Cyclopentadienyl Titanium Imido Compounds and Their Ethylene Polymerization Capability: Control of Molecular Weight Distributions by Imido N-Substituents

Reaction of the previously reported Cp*Ti(NtBu)Cl(py) (1) with bulky ortho-substituted anilines ArNH2 afforded the corresponding aryl imido derivatives Cp*Ti(NAr)Cl(py) (Ar = 2,6-C6H3iPr2 (2), 2,6-C6H3Br2 (3), 2-C6H4tBu (4), and 2-C6H4iPr (5)). Reaction of 2 with B(C6F5)3 in C6D6 or heating in vacuo at 200 °C afforded the imido-bridged dimer Cp*2Ti2(μ-N-2,6-C6H3iPr2)2Cl2 (8). Activation of 1−5 with MAO gave moderately active catalyst systems for the polymerization of ethylene in contrast to the previously reported, highly active titanium imido systems Ti(Me3[9]aneN3)(NR)Cl2/MAO and Ti{HC(Me2pz)3}(NR)Cl2/MAO, which are isolobal and isoelectronic with 1−5. The Cp*-supported precatalyst productivities were sensitive to both the imido N-substituents and initial precatalyst/cocatalyst concentrations. Depending upon the imido N-substituents and initial precatalyst/cocatalyst concentrations, polyethylene with unimodal (either rather low or very high molecular weight) or bimodal molecular weight distributions can...

Organic‐Inorganic Hybrids: Preparation and Structural Characterization of (Bu4N)2[Mo6O17(NAr)2] and (Bu4N)2[Mo6O18(NAr)] (Ar = o‐CH3C6H4)

AbstractIn the presence of N, N′‐dicyclohexylcarbodiimide (DCC), (Bu4N)2[Mo6O18(NAr)] (1) and (Bu4N)2[Mo6O17(NAr)2] (2), Ar = o‐CH3C6H4, have been synthesized via the reaction of [α‐Mo8O26]4— with o‐toluidine. If the hydrochloride salt of o‐toluidine was added into the reactive mixture, only the monofunctionalized imido derivative of [Mo6O19]2— was obtained; the bifunctionalized derivative of [Mo6O19]2— was exclusively synthesized in the presence of non‐protonated o‐toluidine. The molecular and crystal structures of the hybrid compounds 1 and 2 were determined by X‐ray single crystal diffraction, and their UV, IR and NMR spectra were compared. Additionally, a possible reaction mechanism was proposed.