Four-electron reduction of dinitrogen during solution disproportionation of the organodimetallic (η-C5Me4R)2Ta2(µ-Cl)4(R = Me, Et) to a new µ-η1,η1-N2 complex and odd-electron organotrimetallic cluster

Lee, Ting Yu; Wooten, Alfred J.; Luci, Jeffrey J.; Swenson, Dale C.; Messerle, Louis

doi:10.1039/b508148c

Cited by 14 publications

(15 citation statements)

References 46 publications

(32 reference statements)

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“…120 The N−N 49). 122 Structural characterization by X-ray crystallography of 65-Et evidence a zigzag Ta 2 N 2 core with a Ta−N−N angle of 166.3(4)°, a N−N distance of 1.280(6) Å, and a short Ta−N distance of 1.804(3) Å. Extending to pseudohalides, Takada and Kinoshita reported [Cp*Ta(SC 6 H 4 Me) 2 ](μ-1,2-N 2 ), 66, which was synthesized in a one pot reaction containing Cp*TaCl 4 , di-p-tolyl disulfide, and KC 8 .…”

Section: Ligand Systems Unique To Vanadium−dinitrogen Complexesmentioning

confidence: 99%

Activation of Dinitrogen by Polynuclear Metal Complexes

et al. 2020

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Activation of dinitrogen plays an important role in daily anthropogenic life, and the processes by which this fixation occurs have been a longstanding and significant research focus within the community. One of the major fields of dinitrogen activation research is the use of multimetallic compounds to reduce and/or activate N2 into a more useful nitrogen-atom source, such as ammonia. Here we report a comprehensive review of multimetallic-dinitrogen complexes and their utility toward N2 activation, beginning with the d-block metals from Group 4 to Group 11, then extending to Group 13 (which is exclusively populated by B complexes), and finally the rare-earth and actinide species. The review considers all polynuclear metal aggregates containing two or more metal centers in which dinitrogen is coordinated or activated (i.e., partial or complete cleavage of the N2 triple bond in the observed product). Our survey includes complexes in which mononuclear N2 complexes are used as building blocks to generate homo- or heteromultimetallic dinitrogen species, which allow one to evaluate the potential of heterometallic species for dinitrogen activation. We highlight some of the common trends throughout the periodic table, such as the differences between coordination modes as it relates to N2 activation and potential functionalization and the effect of polarizing the bridging N2 ligand by employing different metal ions of differing Lewis acidities. By providing this comprehensive treatment of polynuclear metal dinitrogen species, this Review aims to outline the past and provide potential future directions for continued research in this area.

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Section: Ligand Systems Unique To Vanadium−dinitrogen Complexesmentioning

confidence: 99%

Activation of Dinitrogen by Polynuclear Metal Complexes

et al. 2020

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“…Given the outcome of the attempt to form amidate-stabilized dinitrogen complexes by reduction, and the inability to access azophilic hydride complexes, we revised our strategy and examined a preformed dinitrogen complex that already includes the Cp*TaCl 2 fragment, namely the dinuclear derivative, [Cp*TaCl 2 ] 2 (m-N 2 ) (6). 43 Reduction of Cp*TaCl 4 with Na/Hg under N 2 , or dehydrochlorination of the hydrazine adduct [(C 5 Me 5 )TaCl 4 ] 2 (m-N 2 H 4 ), gives the dinuclear dinitrogen complex 6. Due to the success of the aforementioned salt metathesis reaction (Scheme 1), two equivalents of the amidate sodium salts 2a,b were reacted with 6 to yield the corresponding dinuclear dinitrogen complexes 7a,b (Scheme 4); spectroscopic and analytical data of the resultant complexes are consistent with the proposed structure.…”

Section: Amidate Supported Dinitrogen Complexesmentioning

confidence: 99%

Oxygenextrusion from amidate ligands to generate terminal TaO units under reducing conditions. How to successfully use amidate ligands in dinitrogen coordination chemistry

et al. 2012

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A series of mixed Cp* amidate tantalum complexes Cp*Ta(RNC(O)R')X(3) (where R = Me(2)C(6)H(3), (i)Pr, R' = (t)Bu, Ph, X = Cl, Me) have been prepared via salt metathesis and their fundamental reactivities under reducing conditions have been explored. Reaction of the tantalum chloro precursors with potassium graphite under N(2) or Ar leads to the stereoselective formation of the terminal tantalum oxo species, Cp*Ta=O(η(2)-RN=CR')Cl. This represents the formal extrusion of oxygen from the amidate ligand to the reduced tantalum center and is accompanied by the formation of the iminoacyl fragment bound to Ta(v). Amidate dinitrogen complexes, [Cp*TaCl(RNC(O)(t)Bu)](2)(μ-N(2)) (where R = Me(2)C(6)H(3), (i)Pr) were synthesized via salt metathesis from the known [Cp*TaCl(2)](2)(μ-N(2)) precursor, establishing that amidate ligands can support dinitrogen complexes, but not the reduction process often necessary for their synthesis.

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“…127 , 128 The complexes resulting from the first Si-H bond addition across the TaN bond could be isolated. When an excess of 130 The chloride ligands could be substituted to synthesize the amidate complexes, with elongated NN bond (1.292(4)Å). 131 Alternatively, reduction of the Cp*TaCl 4 with an excess of KC 8 (5 equiv.)…”

Section: Scheme 34mentioning

confidence: 99%