Coordination and reactivity of acetonitrile in tungsten(IV) complexes: oxidation, methylation and dimerization of coordinated acetonitrile

Cross, Jeffrey L.; Garrett, Andrew; Crane, Todd W.; White, Peter S.; Templeton, Joseph L.

doi:10.1016/j.poly.2004.09.008

Cited by 30 publications

(23 citation statements)

References 74 publications

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“…[17] A relevant series of tungsten-nitrile complexes, showing either s-or p-bonding, has been recently reported by Templetons group. [18] In this context, our group has also published a series of reports regarding the activation of aryl, heteroaryl and alkyl cyanides using the nickel(0) fragment [(dippe)Ni], that yield p-bonded h 2 -NCR complexes, such as [(dippe)Ni(h 2 -NCR)] (R ¼ phenyl or methyl; 1 and 2), respectively. [19] In the cases of aryl and heteroaryl cyanides, oxidative addition of the C À CN bond of the nitrile to the nickel(0) proceeds with a mild warming, forming the corresponding nickel(II) complexes.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

2006

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Abstract:The homogeneous catalytic hydration of benzo-and acetonitrile under thermal conditions was achieved using nickel(0) compounds of the type [(dippe)Ni(h 2 -NCR)] with R ¼ phenyl or methyl (compounds 1 and 2, respectively), as the specific starting intermediates. Alternatively, the complexes may be prepared in situ by direct reaction of the precursor [(dippe)NiH] 2 (3) with the respective nitrile. Hydration appears to occur homogeneously, as tested by mercury drop experiments, producing benzamide and acetamide, respectively. Addition of Bu 4 NI did not lead to catalysis inhibition, suggesting the prevalence of Ni (0) intermediates during catalysis. Hydration using analogous complexes of 3, such as [(dtbpe)NiH] 2 (4) and [(dcype)NiH] 2 (5) was also addressed.

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Section: Introductionmentioning

confidence: 99%

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

2006

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“…13 Although we refer to the N-CO 2 functionality as an N-bound carbamate, it may be thought of as an imido ligand bearing a CO 2 substituent and is closely related to the acylimido functional group, for which a number of examples have been synthesized and structurally characterized. [14][15][16][17][18][19][20][21]…”

mentioning

confidence: 99%

Ligand-Based Reduction of CO₂ to CO Mediated by an Anionic Niobium Nitride Complex

Silvia

Cummins

2010

J. Am. Chem. Soc.

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The terminal nitride anion complex [Na][N[triple bond]Nb(N[(t)Bu]Ar)(3)] ([Na][1], Ar = 3,5-Me(2)C(6)H(3)) reacts quantitatively with CO(2) to give the carbamate complex [Na][O(2)CN[triple bond]Nb(N[(t)Bu]Ar)(3)] ([Na][O(2)C-1]). The structure of [Na][O(2)C-1] as the bis-12-crown-4 solvate, as determined by X-ray crystallography, displays a unique N-bound carbamate ligand without any metal-oxygen interactions. When treated with organic acid anhydrides or acid chlorides, complex [Na][O(2)C-1] reacts via salt elimination to give the five-coordinate complexes (RC(O)O)(OCN)Nb(N[(t)Bu]Ar)(3) (R-2, R = Me, (t)Bu, F(3)C). We show that complexes R-2 yield the starting complex [Na][1] with concomitant release of CO upon two-electron reduction. This series of reactions constitutes a closed cycle for the conversion of CO(2) to CO mediated by a terminal nitride anion complex.

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“…As summarized in Scheme , treatment of the ditungsten end-on-bridged dinitrogen compound {Cp*[N( i Pr)C(Me)N( i Pr)]W} 2 (μ-η 1 :η 1 -N 2 ) ( 3 ) with excess NCMe under a CO atmosphere did not produce the desired monocarbonyl mono(acetonitrile) product; rather, the ditungsten “bridging” diimido complex {Cp*[N( i Pr)C(Me)N( i Pr)]W} 2 [μ-η 1 :η 1 -NC(Me)C(Me)N] ( 4 ), in which two acetonitrile ligands have undergone reductive coupling, was obtained in high yield instead . In benzene- d 6 solution, complex 4 displays C s symmetry, as determined by 1 H NMR spectroscopy, in which only a single methyl group resonance for the bridging diimido fragment is observed.…”

Section: Resultsmentioning

confidence: 99%

Small-Molecule Activation within the Group 6 Complexes (η⁵-C₅Me₅)[N(ⁱPr)C(Me)N(ⁱPr)]M(CO)(L) for M = Mo, W and L = N₂, NCMe, η²-Alkene, SMe₂, C₃H₆O

et al. 2016

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A series of midvalent monocyclopentadienyl monoamidinate (CPAM) group 6 complexes of the general formula Cp*[N( i Pr)C(Me)N( i Pr)]M(CO)(L) (II), where Cp* = η 5 -C 5 Me 5 and M = Mo, W, have been prepared, and most of them have been structurally characterized. Treatment of the ditungsten "end-on-bridged" dinitrogen complex {Cp*[N( i Pr)C(Me)N( i Pr)]W} 2 (μ-η 1 :η 1 -N 2 ) (3) with excess NCMe under a CO atmosphere produced the ditungsten bridging diimido complex {Cp*[N( i Pr)C(Me)N( i Pr)]W} 2 [μ-with excess alkene provided Cp*[N( i Pr)C(Me)N( i Pr)]-M(CO)(L) for M = Mo and L = η 2 -ethene (8), M = W and L = η 2 -ethene (9), M = Mo and L = η 2 -norbornene (10), M = W and L = η 2 -norbornene (11), M = W and L = η 2 -cyclopentene (12), M = Mo and L = η 2 -cyclopentene (13), and M = Mo and L = η 2styrene (14). When isobutene was employed as the alkene, C−H bond activation occurred to produce Cp*[N( i Pr)C(Me)-N( i Pr)]W(H)(η 3 -C 4 H 7 ) (15). Photolysis of 7 in the presence of SMe 2 provided Cp*[N( i Pr)C(Me)N( i Pr)]W[κ-C,O-C(O)Me](SMe) (16) through oxidative C−S bond activation of a coordinated SMe 2 , followed by 1,1-carbonyl migratory insertion into the new W−C bond. Finally, reaction of 1a with propylene oxide (C 3 H 6 O) provided the 16-electron complex Cp*[N( i Pr)C(Me)N( i Pr)]Mo[C(O)CH(Me)CH 2 O] (19) via similar oxidative C−O bond activation of coordinated C 3 H 6 O, followed by 1,1-carbonyl migratory insertion into the Mo−C bond of an intermediate metallaoxetane. Under a CO atmosphere, 19 is converted to the 18-electron complex Cp*[N( i Pr)C(Me)N( i Pr)]Mo[C(O)CH(Me)CH 2 O](CO) (20). These results provide additional support for the development of new stoichiometric and catalytic transformations that are mediated by CPAM group 6 metal complexes and that are relevant to the goal of small-molecule fixation.

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Coordination and reactivity of acetonitrile in tungsten(IV) complexes: oxidation, methylation and dimerization of coordinated acetonitrile

Cited by 30 publications

References 74 publications

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

Ligand-Based Reduction of CO₂ to CO Mediated by an Anionic Niobium Nitride Complex

Small-Molecule Activation within the Group 6 Complexes (η⁵-C₅Me₅)[N(ⁱPr)C(Me)N(ⁱPr)]M(CO)(L) for M = Mo, W and L = N₂, NCMe, η²-Alkene, SMe₂, C₃H₆O

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Coordination and reactivity of acetonitrile in tungsten(IV) complexes: oxidation, methylation and dimerization of coordinated acetonitrile

Cited by 30 publications

References 74 publications

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

Catalytic Hydration of Benzonitrile and Acetonitrile using Nickel(0)

Ligand-Based Reduction of CO2 to CO Mediated by an Anionic Niobium Nitride Complex

Small-Molecule Activation within the Group 6 Complexes (η5-C5Me5)[N(iPr)C(Me)N(iPr)]M(CO)(L) for M = Mo, W and L = N2, NCMe, η2-Alkene, SMe2, C3H6O

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Ligand-Based Reduction of CO₂ to CO Mediated by an Anionic Niobium Nitride Complex

Small-Molecule Activation within the Group 6 Complexes (η⁵-C₅Me₅)[N(ⁱPr)C(Me)N(ⁱPr)]M(CO)(L) for M = Mo, W and L = N₂, NCMe, η²-Alkene, SMe₂, C₃H₆O