Transformation of Coordinated Dinitrogen by Reaction with Dihydrogen and Primary Silanes

Fryzuk, Michael D.; Love, Jason B.; Rettig, Steven J.; Young, Victor G.

doi:10.1126/science.275.5305.1445

Cited by 397 publications

(358 citation statements)

References 28 publications

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“…{[P 2 N 2 ]Zr} 2 (µ-H) 4 was prepared 3 from [P 2 N 2 ]ZrCl 2 , using C 8 K as a reducing agent, under 4 atm of H 2 . Interestingly, it does not appear to be possible to form a zirconium hydride from [P 2 N 2 ]ZrMe 2 .…”

Section: Preparation and Structure Of [P 2 N 2 ]Hfme 2 (6)mentioning

confidence: 99%

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Reduction of hafnium(IV) complexes in the presence of molecular nitrogen: Attempts to form dinitrogen complexes of the heaviest group 4 element

Fryzuk¹,

Corkin²,

Patrick³

2003

Can. J. Chem.

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The reaction of [P 2 N 2 ]Li 2 (dioxane) 2 with HfCl 4 (THF) 2 (where [P 2 N 2 ] = PhP(CH 2 SiMe 2 NSiMe 2 CH 2 ) 2 PPh) results in the formation of the hafnium dichloride complex [P 2 N 2 ]HfCl 2 (1). The behaviour of 1 as a potential precursor in the generation of a dinitrogen coordination complex is described. Reduction of 1 with potassium-graphite (C 8 K), under dinitrogen, under a variety of conditions led to a number of products, one of which is the dinuclear derivative with bridging P-phenyl groups that has the general formula {[P 2 N 2 ]Hf} 2 (2). Reduction of the hafnium diiodide [P 2 N 2 ]HfI 2 (3) -prepared via the reaction of 1 with excess Me 3 SiI -with C 8 K results in the formation of ([P 2 N 2 ]Hf) 2 (µ-η 2 :η 2 -N 2 ) (4) as the major product of the reaction, while {[P 2 N 2 ]Hf} 2 (2) and [P 2 N 2 ]Hf(C 7 H 8 ) (5) appear to be minor products. Reaction of 1 with 2 equiv of MeMgCl gives [P 2 N 2 ]HfMe 2 (6), which, upon exposure to an atmosphere of H 2 , gives the hafnium tetrahydride {[P 2 N 2 ]Hf} 2 (m-H) 4 (7).Résumé : La réaction du [P 2 N 2 ]Li 2 (dioxane) 2 avec le HfCl 4 (THF) 2 {dans lequel [P 2 N 2 ] = PhP(CH 2 SiMe 2 NSiMe 2 CH 2 ) 2 PPh} conduit à la formation du complexe de dichlorure d'hafnium, [P 2 N 2 ]HfCl 2 (1). On décrit le comportement du complexe 1 comme précurseur potentiel pour générer un complexe de coordination du diazote. La déduction de 1 à l'aide de potassium sur graphite (C 8 K), sous atmosphère de diazote, dans diverses conditions expérimentales conduit à la formation d'un certain nombre de produits, dont l'un est un dérivé dinucléaire de formule générale {[P 2 N 2 ]Hf} 2 (2) portant des groupes P-phényles agissant comme ponts. La réduction par le C 8 K du complexe de diiodure d'hafnium, [P 2 N 2 ]HfI 2 (3), préparé par le biais d'une réaction de 1 avec un excès de Me 3 SiI, conduit à la formation du complexe {([P 2 -N 2 ]Hf) 2 (µ-η 2 :η 2 -N 2 ) (4) comme produit majeur de la réaction alors qu'il semble y avoir formation {[P 2 N 2 ]Hf} 2 (2) et de [P 2 N 2 ]Hf(C 7 H 8 ) (5) comme sous-produits. La réaction de 1 avec deux équivalents de MeMgCl conduit à la formation de [P 2 N 2 ]HfMe 2 (6) qui, mis dans une atmosphère de H 2 , fournit le tétrahydrure d'hafnium, {[P 2 N 2 ]Hf} 2 (µ-H) 4 (7).

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Section: Preparation and Structure Of [P 2 N 2 ]Hfme 2 (6)mentioning

confidence: 99%

“…The zirconium complex has been shown to add H 2 and primary silanes with concomitant formation of N-H and NSi bonds, respectively (4). We reasoned that access to the hafnium dinitrogen complex congener might allow for similar reactivity and even perhaps different reactivity patterns.…”

Section: Introductionmentioning

confidence: 98%

Reduction of hafnium(IV) complexes in the presence of molecular nitrogen: Attempts to form dinitrogen complexes of the heaviest group 4 element

Fryzuk¹,

Corkin²,

Patrick³

2003

Can. J. Chem.

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“…Observation of the N-H functionality marked the first report of such a transformation by addition of H 2 to a dinitrogen complex[53]. Further stoichiometric functionalizations of coordinated dinitrogen led to a variety of transformations involving heterolytic bond cleavage, as illustrated in Scheme 5.For example, addition of n-butylsilane resulted in the formation of an N-Si bond as found in ([P 2 N 2 ]Zr) 2 (N 2 Si n BuH 2 )(H) (5.4)[53]. This complex was characterized by X-ray crystallography and bears a long N-N bond distance of 1.530(4) Å (Scheme 5).…”

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confidence: 96%

Dinitrogen activation by group 4 and group 5 metal complexes supported by phosphine-amido containing ligand manifolds

Burford

Yeo

Fryzuk

2017

Coordination Chemistry Reviews

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104

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“…Stoichiometric cleavage of the strong N-N bond has been observed for groups 5 and 6 metal complexes (20)(21)(22)(23)(24)(25), certain dinuclear zirconium dinitrogen complexes have been found to react with H 2 to generate N-H bonds (26)(27)(28), and terminal alkynes have been found to react with coordinated N 2 in a side-on bound dizirconium complex to generate a N-C bond (29). These processes have expanded the toolbox of fundamental reactions for coordinated dinitrogen.…”

mentioning

confidence: 97%

Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen

Spencer

Patrick²,

Fryzuk³

2006

Proc. Natl. Acad. Sci. U.S.A.

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Transformation of Coordinated Dinitrogen by Reaction with Dihydrogen and Primary Silanes

Abstract: ReactionwithDihydrogenandPrimarySilanes t e t r a h~d r o f~~~a n , a n d~h = p h e n r l } ( l~) t o ZrCl,(THT), ( T H T = t e t r a h~d r o t h~o -

Cited by 397 publications

References 28 publications

Reduction of hafnium(IV) complexes in the presence of molecular nitrogen: Attempts to form dinitrogen complexes of the heaviest group 4 element

Reduction of hafnium(IV) complexes in the presence of molecular nitrogen: Attempts to form dinitrogen complexes of the heaviest group 4 element

Dinitrogen activation by group 4 and group 5 metal complexes supported by phosphine-amido containing ligand manifolds

Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen

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