Reactions of Metal Carbonyls with the Azide Ion and – vice versa – Reactions of Azido Complexes with Carbon Monoxide: Isocyanato Complexes. Analogous Reactions in NO+/N3– Transition Metal Chemistry [1]

Beck, Wolfgang; Fehlhammer, Wolf Peter

doi:10.1002/zaac.200900473

Cited by 8 publications

(6 citation statements)

References 130 publications

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“…This reaction occurred both in the absence and presence of light, implying the direct (intramolecular) attack of CO onto the azide with expulsion of N 2 . [15] Addition of PMe 3 or PPh 3 to asolution of 2 in THF did not result in any appreciable reactivity.…”

mentioning

confidence: 89%

“…Theuse of H 2 as trapping agent did not lead to the parent Niamido species,but instead the known Ni(H)(PNP) complex [13] was observed. NH 3 was detected by 15 NNMR spectroscopy and spectrophotometric assay analysis (SI). Use of D 2 resulted in ND 3 .T he NH 3 and the Ni-hydride may originate from reaction of H 2 with the transient nitrido,b ut other pathways for their formation cannot be excluded at this point.…”

Section: Angewandte Chemiementioning

confidence: 99%

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CH Activation of Benzene by a Photoactivated Ni^II(azide): Formation of a Transient Nickel Nitrido Complex

Vreeken

Siegler²,

Bruin

et al. 2015

Angew Chem Int Ed

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Photochemical activation of nickel-azido complex 2 [Ni(N3)(PNP)] (PN(H)P=2,2'-di(isopropylphosphino)-4,4'-ditolylamine) in neat benzene produces diamagnetic complex 3 [Ni(Ph)(PN(P)N(H))], which is crystallographically characterized. DFT calculations support photoinitiated N2-loss of the azido complex to generate a rare, transient Ni(IV) nitrido species, which bears significant nitridyl radical character. Subsequent trapping of this nitrido through insertion into the Ni-P bond generates a coordinatively unsaturated Ni(II) imidophosphorane P=N donor. This species shows unprecedented reactivity toward 1,2-addition of a C-H bond of benzene to form 3. The structurally characterized chlorido complex 4 [Ni(Cl)(PN(P)N(H))] is generated by reaction of 3 with HCl or by direct photolysis of 2 in chlorobenzene. This is the first report of aromatic C-H bond activation by a trapped transient nitrido species of a late transition metal.

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mentioning

confidence: 89%

Section: Angewandte Chemiementioning

confidence: 99%

CH Activation of Benzene by a Photoactivated Ni^II(azide): Formation of a Transient Nickel Nitrido Complex

Vreeken

Siegler²,

Bruin

et al. 2015

Angew Chem Int Ed

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“…10 Recently, considerable attention has been attracted by the metal-mediated N-N multiple bond cleavage. Many achievements have been made for dinitrogen, 11 diazoalkane 12 and azide 13 compounds. Kuwata has reported the N-N bond cleavage of hydrazines catalyzed by a bifunctional complex of iron with a multiproton-responsive pincer-type ligand.…”

Section: Introductionmentioning

confidence: 99%

Theoretical mechanism studies on the competitive CO-induced N–N bond cleavage of N2O with N–O bond cleavage mediated by (η5-C5Me5)Mo[N(iPr)C(Me)N(iPr)](CO)2

Wang

2013

Dalton Trans.

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The reaction mechanism for CO-induced reduction of N2O mediated by (η(5)-C5Me5)Mo[N((i)Pr)C(Me)N((i)Pr)](CO)2 is studied using density functional theory (DFT). Two competitive pathways for the N-O and N-N bond cleavage are investigated in detail. The former generates N2, CO and a coproduct terminal Mo oxo complex, which is attacked by two CO to recycle the catalyst via oxygen atom transfer (OAT) in a four-step process. The latter contains three steps yielding a nitrosyl, isocyanate complex. The N-N bond cleavage occurs in step 3. The barriers of the key steps are numerically similar in the two paths. The calculated proportion of products is consistent with the experiment. The competition of N-O and N-N bond cleavage is also supported by NBO analysis.

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“…To account for the present results, we currently favor the mechanism shown in Scheme , which is similar to that previously proposed by Bergman and co-workers for CO-induced N–N bond cleavage of a diazoalkane by the Cp* 2 Ti fragment. Further precedent exists for end-on κ- N coordination of N 2 O to a vanadium center, and for isocyanate formation via intramolecular attack on a metal-bound CO group is provided by related metal azide chemistry …”

mentioning

confidence: 99%

Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide As Mediated by a Mo(II)/Mo(IV) Catalytic Cycle

et al. 2011

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In the presence of CO, facile N-N bond cleavage of N(2)O occurs at the formal Mo(II) center within coordinatively unsaturated mononuclear species derived from Cp*Mo[N((i)Pr)C(Me)N((i)Pr)](CO)(2) (Cp* = η(5)-C(5)Me(5)) (1) and {Cp*Mo[N((i)Pr)C(Me)N((i)Pr)]}(2)(μ-η(1):η(1)-N(2)) (9) under photolytic and dark conditions, respectively, to produce the nitrosyl, isocyanate complex Cp*Mo[N((i)Pr)C(Me)N((i)Pr)](κ-N-NO)(κ-N-NCO) (7). Competitive N-O bond cleavage of N(2)O proceeds under the same conditions to yield the Mo(IV) terminal metal oxo complex Cp*Mo[N((i)Pr)C(Me)N((i)Pr)](O) (3), which can be recycled to produce more 7 through oxygen-atom-transfer oxidation of CO to produce CO(2).

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Reactions of Metal Carbonyls with the Azide Ion and – vice versa – Reactions of Azido Complexes with Carbon Monoxide: Isocyanato Complexes. Analogous Reactions in NO⁺/N₃^– Transition Metal Chemistry [1]

Cited by 8 publications

References 130 publications

CH Activation of Benzene by a Photoactivated Ni^II(azide): Formation of a Transient Nickel Nitrido Complex

CH Activation of Benzene by a Photoactivated Ni^II(azide): Formation of a Transient Nickel Nitrido Complex

Theoretical mechanism studies on the competitive CO-induced N–N bond cleavage of N2O with N–O bond cleavage mediated by (η5-C5Me5)Mo[N(iPr)C(Me)N(iPr)](CO)2

Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide As Mediated by a Mo(II)/Mo(IV) Catalytic Cycle

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Reactions of Metal Carbonyls with the Azide Ion and – vice versa – Reactions of Azido Complexes with Carbon Monoxide: Isocyanato Complexes. Analogous Reactions in NO+/N3– Transition Metal Chemistry [1]

Cited by 8 publications

References 130 publications

CH Activation of Benzene by a Photoactivated NiII(azide): Formation of a Transient Nickel Nitrido Complex

CH Activation of Benzene by a Photoactivated NiII(azide): Formation of a Transient Nickel Nitrido Complex

Theoretical mechanism studies on the competitive CO-induced N–N bond cleavage of N2O with N–O bond cleavage mediated by (η5-C5Me5)Mo[N(iPr)C(Me)N(iPr)](CO)2

Carbon Monoxide-Induced N–N Bond Cleavage of Nitrous Oxide That Is Competitive with Oxygen Atom Transfer to Carbon Monoxide As Mediated by a Mo(II)/Mo(IV) Catalytic Cycle

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Reactions of Metal Carbonyls with the Azide Ion and – vice versa – Reactions of Azido Complexes with Carbon Monoxide: Isocyanato Complexes. Analogous Reactions in NO⁺/N₃^– Transition Metal Chemistry [1]

CH Activation of Benzene by a Photoactivated Ni^II(azide): Formation of a Transient Nickel Nitrido Complex

CH Activation of Benzene by a Photoactivated Ni^II(azide): Formation of a Transient Nickel Nitrido Complex