Synthesis and DFT, Multinuclear Magnetic Resonance, and X-ray Structural Studies of Iminoacyl Imido Hydridotris(3,5-dimethylpyrazolyl)borate Niobium and Tantalum(V) Complexes

Galajov, Miguel; García, Carlos J. Gómez; Gómez, Manuel; Gómez‐Sal, Pilar; Temprado, Manuel

doi:10.1021/om5002028

Cited by 8 publications

(2 citation statements)

References 96 publications

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“…In addition to the plausible formation of the isomers analyzed in Schemes and , the rotation of the iminoacyl ligands lead to different isomers ( endo – exo ) as described in Scheme for compounds anti - 4a (R′ = Me) and anti - 3a (R′ = t Bu) and as previously reported for other η 2 -iminoacyl complexes. ,− …”

Section: Results and Discussionsupporting

confidence: 55%

Structural Diversity in the Reactions of Dimetallic Alkyl Titanium Oxides with Isonitriles and Nitriles

et al. 2021

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A detailed study of the reaction of the dinuclear [{Ti(η5-C5Me5)R2}2(μ-O)] (R = Me 1, CH2Ph 2) compounds with a series of organic isonitriles (R′NC, R′ = tBu, iPr, CH2SiMe3, Xyl) (Xyl = 2,6-Me2C6H3) and nitriles (R′CN, R′ = tBu, iPr, SiMe3) has been carried out. Single-crystal X-ray structural studies revealed a variety of reactivity and structural moieties. Theoretical calculations (density functional theory, DFT) were used to understand the mechanism of some uncommon reactions observed experimentally. Reactions of 1 and 2 with isocyanides tBuNC, iPrNC, and Me3SiCH2NC led to the formation of dimetallic η2-iminoacyl species [{Ti(η5-C5Me5)(R′NCR)R}2(μ-O)] (R = Me, R′ = tBu 3, iPr 4, CH2SiMe3 5; R = CH2Ph, R′ = CH2SiMe3 6). Complex 4 underwent net rearrangements at room temperature to give the imido-vinylamido derivative [Ti2(η5-C5Me5)2(μ-O)(μ-NiPr) {N(iPr)CMeCMe2}Me] (7), whereas the reaction of complex 2 with XylNC rendered the NC bond cleavage product [{Ti(η 5 -C5Me5)(CHCHPh)}(μ-O)(μ-κ 2 -N,CN(MeC6H3)CH2){Ti(η 5 -C5Me5)}] (8). The reactions of 1 with nitriles tBuCN and iPrCN gave the ketimido products [{Ti(η 5 -C5Me5)Me(CN(Me)R′)}2(μ-O)] (R′ = tBu 9, iPr 10), whereas the analogous processes with 2 gave the alkenyl-imido complexes [{Ti(η 5 -C5Me5)(CH2Ph)2}(μ-O){Ti(η 5 -C5Me5)(NC(R′)C(H)Ph)(NCR′)}] (R′ = tBu 11, iPr 12) with the concomitant coordination of a nitrile molecule. Complex 1 reacts with Me3SiCN to afford the nitrile–isonitrile isomerization product [{Ti(η 5 -C5Me5)Me2}(μ-O){Ti(η5-C5Me5)(κ 2 -C,N-Me2CNSiMe3)(CNSiMe3)] (13).

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Section: Results and Discussionsupporting

confidence: 55%

Structural Diversity in the Reactions of Dimetallic Alkyl Titanium Oxides with Isonitriles and Nitriles

et al. 2021

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“…The chemical shifts of the 15 N nitride resonances in the 15 N NMR spectra of 1- 15 N , 2- 15 N , and 3- 15 N suggest the relative electron density of the nitride ligands, at least to a first approximation. In organic compounds, 15 N NMR chemical shifts have been shown to be correlated to various chemical properties, including Lewis basicity. − We wondered whether the 15 N NMR chemical shifts of the nitride ligands could thus be an estimate of the relative electron richness of these ligands and, by extension, be used to predict reactivity. Functionalization of the amide in 1- 15 N to form a nitroxide ( 2- 15 N ) or protonated amide ( 3- 15 N ) both shift the nitride 15 N resonance downfield, suggesting a decrease in Lewis basicity.…”

Section: Resultsmentioning

confidence: 99%

Chemical Oxidation of a Coordinated PNP-Pincer Ligand Forms Unexpected Re–Nitroxide Complexes with Reversal of Nitride Reactivity

et al. 2019

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Because of the thermodynamic demands of N2 cleavage, N2-derived nitride complexes are often unreactive. The development of multistep N2 functionalization reactions hinges on methods for modulating nitride reactivity with supporting ligands. Here, we describe the reactions of N2-derived Re–nitride complexes, including the first Re nitrides supported by a nitroxide-containing pincer ligand, and unusual examples of Re6+–nitride complexes. The previously reported N2-derived complex (PNP)Re(N)(Cl) (PNP = N(CH2CH2PtBu2)2) can be oxidized by O atom transfer to the backbone amide to form a novel nitroxide-pincer complex or by 1e– to form a rare S = 1/2 Re6+–nitride complex. The Re–nitrido interaction in a series of Re- and ligand-oxidized complexes is characterized using 15N NMR spectroscopy, IR spectroscopy, and DFT calculations, and shows changes in the Re–N bond order from both ligand- and metal-centered oxidations. Chemical oxidation of the supporting ligand to form a nitroxide-pincer ligand results in subtle electronic changes at Re and a more electron-deficient nitride ligand. Combined ligand- and metal-centered oxidation to form a Re6+–nitroxide complex results in a reversal of reactivity at the nitride ligand from nucleophilic to electrophilic. These systematic electronic structure and reactivity studies demonstrate methods for inducing reactivity in N2-derived nitride complexes.

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Polypyrazolylborates and Scorpionates

Fischer

2021

Comprehensive Coordination Chemistry III

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Synthesis and DFT, Multinuclear Magnetic Resonance, and X-ray Structural Studies of Iminoacyl Imido Hydridotris(3,5-dimethylpyrazolyl)borate Niobium and Tantalum(V) Complexes

Cited by 8 publications

References 96 publications

Structural Diversity in the Reactions of Dimetallic Alkyl Titanium Oxides with Isonitriles and Nitriles

Structural Diversity in the Reactions of Dimetallic Alkyl Titanium Oxides with Isonitriles and Nitriles

Chemical Oxidation of a Coordinated PNP-Pincer Ligand Forms Unexpected Re–Nitroxide Complexes with Reversal of Nitride Reactivity

Polypyrazolylborates and Scorpionates

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