Photochemical reaction of phosphine hydride complexes of molybdenum and tungsten with molecular nitrogen

Pivovarov, A. P.; Gak, Yu. V.; Doronina, T. N.; Makhaev, V. D.; Borisov, A. P.; Borod'ko, Yu. G.

doi:10.1007/bf00950268

Cited by 3 publications

(4 citation statements)

References 8 publications

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“…Second, only a few examples of displacement of metal-hydrides by N 2 are known, typically with the aid of UV irradiation. 76,77 The reverse, the displacement of N 2 by dihydrogen, is more common. 78−80 Addition of succinyl dichloride to [WF(NNH 2 )(dppe) 2 ]-[BF 4 ] yielded the ethanedioylhydrazide(2-) (Scheme 10).…”

Section: Interaction Of N 2 With Transition Metalsmentioning

confidence: 99%

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Beyond Ammonia: Nitrogen–Element Bond Forming Reactions with Coordinated Dinitrogen

2020

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The functionalization of coordinated dinitrogen to form nitrogen–element bonds en route to nitrogen-containing molecules is a long-standing challenge in chemical synthesis. The strong triple bond and the nonpolarity of the N2 molecule pose thermodynamic and kinetic challenges for promoting reactivity. While heterogeneous, homogeneous, and biological catalysts are all known for catalytic nitrogen fixation to ammonia, the catalytic synthesis of more complicated nitrogen-containing organic molecules has far less precedent. The example of silyl radical additions to coordinated nitrogen to form silylamines stands as the lone example of a catalytic reaction involving N2 to form a product other than ammonia. This Review surveys the field of molecular transition metal complexes as well as recent boron examples for the formation of nitrogen–element bonds. Emphasis is placed on the coordination and activation modes of N2 in the various metal compounds from across the transition series and how these structures can rationally inform reactivity studies. Over the past few decades, the field has evolved from the addition of carbon electrophiles in a manner similar to that of protonation reactions to more organometallic-inspired reactivity, including insertions, 1,2-additions, and cycloadditions. Various N–C, N–Si, and N–B bond-forming reactions have been discovered, highlighting that the challenge for catalytic chemistry is not in the reactivity of coordinated dinitrogen but rather removal of the functionalized ligand from the coordination sphere of the metal.

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Section: Interaction Of N 2 With Transition Metalsmentioning

confidence: 99%

“…First, incompatibility of acidic HBF 4 and hydridic LiAlH 4 prevent use in a single reaction vessel. Second, only a few examples of displacement of metal-hydrides by N 2 are known, typically with the aid of UV irradiation. , The reverse, the displacement of N 2 by dihydrogen, is more common. − …”

Section: N–x Bond Formation With Retention Of the N–n Bondmentioning

confidence: 99%

Beyond Ammonia: Nitrogen–Element Bond Forming Reactions with Coordinated Dinitrogen

2020

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“…Therefore, it was of interest to study the mechanism of decomposition of electron excited molecules of the phos phine hydride complexes of transition metals MH 4 L 4 (M = Mo, W; L = PHPh 2 , PMePh 2 , PEtPh 2 , PEt 2 Ph, PBuPh 2 , PPrPh 2 , P(OPr i ) 2 Ph, P(OPr i ) 3 , 1/2 DPPE (DPPE = Ph 2 PCH 2 CH 2 PPh 2 ), and others). In the present work, we studied the kinetics of photodehydrogenation of the phosphine hydride complexes upon irradiation in deu terated benzene (C 6 D 6 ) and cyclohexane (C 6 D 12 ) and the formation of coordinatively unsaturated species from the Mo and W phosphine hydride (MH 4 L 4 ) and phosphine nitrogen (trans M(N 2 ) 2 L 4 ) complexes under the condi tions of stationary and pulse irradiation at 77 and 300 K, respectively.…”

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confidence: 99%

“…Pulse photolysis of a nitrogen saturated benzene solution of trans W(N 2 ) 2 (DPPE) 2 at 300 K: kinetics of changes in the absorbance at λ = 550 nm (D 550 ) after a photolyzing pulse (1); lnD 550(2).…”

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Decomposition of electron-excited molecules of molybdenum and tungsten phosphine hydride and phosphine nitrogen complexes

Pivovarov

2008

Russ Chem Bull

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The kinetics and mechanism of photodehydrogenation of the phosphine hydride complexes MH 4 L 4 (M = Mo, W; L are phosphine ligands) and the formation of coordinatively unsaturated species ML 4 were studied by the absorbance of long wavelength bands with λ max at 450-460 nm appeared in the absorption spectra of the photoproducts. The rate constants of the reactions of the coordinatively unsaturated M(DPPE) 2 species (M = Mo, W; DPPE = Ph 2 PCH 2 CH 2 PPh 2 ) with molecular nitrogen in benzene were determined (k W = 200 s -1 , k Mo = 8700 s -1 ).

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Ammonia synthesis by photocatalytic hydrogenation of a N2-derived molybdenum nitride

et al. 2022

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Photochemical reaction of phosphine hydride complexes of molybdenum and tungsten with molecular nitrogen

Cited by 3 publications

References 8 publications

Beyond Ammonia: Nitrogen–Element Bond Forming Reactions with Coordinated Dinitrogen

Beyond Ammonia: Nitrogen–Element Bond Forming Reactions with Coordinated Dinitrogen

Decomposition of electron-excited molecules of molybdenum and tungsten phosphine hydride and phosphine nitrogen complexes

Ammonia synthesis by photocatalytic hydrogenation of a N2-derived molybdenum nitride

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