A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity

Schendzielorz, Florian; Finger, Markus; Volkmann, Christian; Würtele, Christian; Schneider, Sven

doi:10.1002/ange.201604917

Cited by 23 publications

(3 citation statements)

References 42 publications

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“…Understanding the reactivity of molecular metal nitrides towards hydrogen is very important for providing chemical insights into the formation of ammonia through the Haber-Bosch process. 42 Despite this, only a few examples of nitride reactivity towards H2 have been reported, 8,19,[43][44][45][46] with the majority using terminal nitride species. To date, only the bimetallic nitride complexes (L3)Fe(μ-N)Fe(L3) (L3 = [PhB(CH2PPh2)3] -) and {Cs[U(OSi(O t Bu)3)3]2(μ-N)} have been shown capable of heterolytically cleaving dihydrogen to give bridging M2(μ-NH)(μ-H) products.…”

Section: Resultsmentioning

confidence: 99%

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H₂

et al. 2020

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Room temperature photolysis of the bis(azide)cobaltate(II) complex [Na(THF)x] [( ket guan)Co(N3)2] ( ket guan = [( t Bu2CN)C(NDipp)2] -, Dipp = 2,6-diisopropylphenyl) (3a) in THF cleanly forms the binuclear cobalt nitride [Na(THF)4{[( ket guan)Co(N3)]2(μ-N)}]n (1). Compound 1 represents the first example of an isolable, bimetallic cobalt nitride complex, and it has been fully characterized by spectroscopic, magnetic, and computational analyses. Density functional theory supports a Co III =N=Co III canonical form with significant π-bonding between the cobalt centers and the nitride atom. Unlike other Group 9 bridging nitride complexes, no radical character is detected at the bridging N-atom of 1. Indeed, 1 is unreactive towards weak C-H donors and even co-crystallizes with a molecule of cyclohexadiene (CHD) in its crystallographic unit cell to give 1•CHD as a room temperature stable product. Notably, addition of pyridine to 1 or photolyzed solutions of [( ket guan)Co(N3)(py)]2 (4a) leads to destabilization via activation of the nitride unit, resulting in the mixed-valent Co(II)/(III) bridged imido species [( ket guan)Co]2(μ-NH)(μ-N3) (5) formed from intermolecular hydrogen atom abstraction (HAA) of strong C-H bonds (BDE ~ 100 kcal/mol). Kinetic rate analysis of the formation of 5 in the presence of C6H12 or C6D12 gives a KIE = 2.5±0.1, supportive of a HAA formation pathway. The reactivity of our system was further probed by photolyzing C6D6/py-d5 solutions of 4a under an H2 atmosphere (150 psi), which leads to the exclusive formation of the bis(imido) [( ket guan)Co(μ-NH)]2 (6) as a result of dihydrogen activation. These results provide unique insights into the chemistry and electronic structure of late 3d-metal nitrides while providing entryway into C-H activation pathways.

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Section: Resultsmentioning

confidence: 99%

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H₂

et al. 2020

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“…[3,4] High electron count (d ! 4) nitrides are uncommon, [3,5,8] and unknown for early metals. They can display enhanced reactivity,i ncluding nitride hydrogenolysis [3,5g, 8] and carbonylation.…”

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A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

2018

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Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d-electron counts are of interest. A series of terminal Mo nitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first Mo nitrido complex, an early metal nitride with four valence d-electrons. The binding mode of the para-terphenyl diphosphine ancillary ligand changes to stabilize an electronic configuration with a high electron count and a formal M-N bond order of three. Even with an intact Mo≡N bond, this low-valent nitrido complex proves to be highly reactive, readily undergoing N-atom transfer upon addition of CO, releasing cyanate anion.

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“…Although a number of highly reactive metal nitrido complexes are known, such as [Os(terpy)(N)Cl 2 ] + (terpy = 2,2′:6′,2″-terpyridine) and related complexes − and [Ru(N)(salchda)(MeOH)] + (salchda = N , N ′-bis(salicylidene)- o -cyclohexyldiamine dianion; MeOH = methanol), , their N-atom-transfer reactivity is still limited, especially toward inert organic substrates.…”

Section: Introductionmentioning

confidence: 99%

Tunable Luminescent Properties of Tricyanoosmium Nitrido Complexes Bearing a Chelating O^N Ligand

Luo

Cheng

et al. 2020

Inorg. Chem.

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We have recently reported a strongly luminescent osmium(VI) nitrido complex [OsVI(N)(NO2-L)(CN)3]− [HNO2-L = 2-(2-hydroxy-5-nitrophenyl)benzoxazole]. The excited state of this complex readily activates the strong C–H bonds of alkanes and arenes (Commun. Chem. 2019, 2, 40). In this work, we attempted to tune the excited-state properties of this complex by introducing various substituents on the bidentate L ligand. The series of nitrido complexes were characterized by IR, UV/vis, 1H NMR, and electrospray ionization mass spectrometry. The molecular structures of five of the nitrido compounds have been determined by X-ray crystallography. The photophysical and electrochemical properties of these complexes have been investigated. The luminescence of these nitrido complexes in the solid state, in a CH2Cl2 solution, and in a CH2Cl2 solid matrix at 77 K glassy medium clearly shows that these emissions are due to 3LML′CT [L ligand to OsN] phosphorescence. The presence of strongly electron-withdrawing substituents in these complexes enhances the LML′CT emission. Our result demonstrates that the excited-state properties of this novel class of luminescent osmium(VI) nitrido complexes can be fine-tuned by introducing various substituents on the bidentate L ligand.

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A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity

Cited by 23 publications

References 42 publications

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H₂

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H₂

A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

Tunable Luminescent Properties of Tricyanoosmium Nitrido Complexes Bearing a Chelating O^N Ligand

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A Terminal Osmium(IV) Nitride: Ammonia Formation and Ambiphilic Reactivity

Cited by 23 publications

References 42 publications

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H2

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H2

A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

Tunable Luminescent Properties of Tricyanoosmium Nitrido Complexes Bearing a Chelating O^N Ligand

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Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H₂

Isolation of a Bimetallic Cobalt(III) Nitride and Examination of Its Hydrogen Atom Abstraction Chemistry and Reactivity toward H₂