Self‐Assembly of a Tetradecanuclear Iron Nitride Cluster

Bennett, Miriam V.; Holm, R. H.

doi:10.1002/anie.200601570

Cited by 22 publications

(17 citation statements)

References 26 publications

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“…In the single-crystal structures as evident in Figure 1, cluster anions 3a, b exhibit analogous centrosymmetric structures.T he cluster is constituted by connection of ap air of cubane-type subunit via two Fe-N edges in head-to-tail mode to form aFe 2 N 2 rhomb,inwhich both nitride ligands adopt m 4bridging mode.Within the rhomb of 3a,the intra-cubane Fe À Nb ond length on the bridging edge at 1.966 (5) is longer than the other two intra-cubane Fe-N contacts of 1.901(5) and 1.888(5) ,a sw ell as the inter-cubane Fe3-N1 i distance at 1.881 (5) .T he molecule also holds quasi-mirror symmetry upon the plane of Fe3-N1-Fe3 i -N1 i .T he average Fe À Nb ond length within the cubic subunit is 1.918(5) ,b eing slightly shorter than that of 1.936(3) in the reported imide bridged cubane cluster. [49] Theb ond length pattern is indicative of tight binding between subunits and Fe-N distances in this cluster are comparable with those for reported iron-nitride complexes with FeÀNs ingle bond [16,[42][43][44][45] (See Table S2 for alist of FeÀNb onds in selected iron nitride complexes).…”

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confidence: 85%

“…Except for bridging nitride in iron carbonyls,m olecular high-connectivity bridging nitrides in iron complexes have only been realized through self-assembly of (Me 3 Sn) 3 Nw ith [FeCl 4 ] À . [43,44] While these and other iron complexes with bridging nitrides were generated with unpredictable nuclearity and cluster geometries,c luster 3a,b were synthesized by ar edox metathesis pathway with as ubstantial degree of control, in which nitride was mounted at targeted position, demonstrating ap otentially useful synthetic strategy for controlled instalment of monatomic 2p ligand.…”

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confidence: 99%

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Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Zhou

Wang

et al. 2019

Angew Chem Int Ed

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Incorporation of monatomic 2p ligands into the core of iron-sulfur clusters has been researched since the discovery of interstitial carbide in the FeMo cofactor of Mo-dependent nitrogenase,but has proven to be asynthetic challenge.Herein, two distinct synthetic pathwaysa re rationalized to install nitride ligands into targeted positions of W-Fe-S clusters, generating unprecedented nitride-ligated iron-sulfur clusters, namely [(Tp*) 2 W 2 Fe 6 (m 4 -N) 2 S 6 L 4 ] 2À (Tp* = tris(3,5-dimethyl-1-pyrazolyl)hydroborate(1À), L = Cl À or Br À ). 57 Fe Mçssbauer study discloses metal oxidation states of W IV 2 Fe II 4 Fe III 2 with localized electron distribution, which is analogous to the midvalent iron centres of FeMo cofactor at resting state.G ood agreement of Mçssbauer data with the empirical linear relationship for Fe-S clusters indicates similar ligand behaviour of nitride and sulfide in such clusters,p roviding useful reference for reduced nitrogen in an itrogenase-like environment.Scheme 1. Distinct synthetic pathwayso fcluster 3.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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confidence: 85%

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confidence: 99%

Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Zhou

Wang

et al. 2019

Angew Chem Int Ed

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“…Here we summarize the recent advances in this field with a focus on monoand dinuclear complexes; thus, omitting the few rare examples of polynuclear iron-nitrido complexes [77][78][79] .…”

Section: Iron-nitrido Model Complexesmentioning

confidence: 99%

The biology and chemistry of high-valent iron–oxo and iron–nitrido complexes

2012

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selective functionalization of unactivated c-H bonds and ammonia production are extremely important industrial processes. a range of metalloenyzmes achieve these challenging tasks in biology by activating dioxygen and dinitrogen using cheap and abundant transition metals, such as iron, copper and manganese. High-valent iron-oxo and -nitrido complexes act as active intermediates in many of these processes. the generation of well-described model compounds can provide vital insights into the mechanism of such enzymatic reactions. advances in the chemistry of model high-valent iron-oxo and -nitrido systems can be related to our understanding of the biological systems.H igh-valent oxoiron(IV) and formally oxoiron(V) species have been spectroscopically identified as active intermediates in the catalytic cycles of a number of enzymatic systems 1-10 . Haem and non-haem proteins use these reactive intermediates to couple the activation of dioxygen to the oxidation of their substrates. In most cases, an oxygen atom is inserted into an unactivated C-H bond of the substrate; for example, in hydroxylation reactions [1][2][3][4][5][6][7][8][9][10] . However, many other reactions, including halogenation, desaturation, cyclization, epoxidation and decarboxylation, are also known to involve oxoiron species 1,3 . Superoxidized iron complexes with (valence) isoelectronic imido and nitrido ligands, as well as 'surface nitrides' , have also been implicated as key intermediates in the nitrogen atom transfer reactions 11 , the biological synthesis of ammonia by the nitrogenase enzyme 12-16 and the industrial Haber-Bosch process 17 .The generation of well-described model compounds can provide vital insights into the mechanism of such enzymatic reactions. Consequently, considerable effort has been made by synthetic chemists to prepare viable models for the putative reaction intermediates in the catalytic cycles of O 2 and N 2 activating enzymes. In this review, we provide an overview of all high-valent oxoiron and nitridoiron species that have been either identified or proposed as reactive intermediates in biology. Subsequently, we summarize some of the recent advances in bioinorganic chemistry that have led to the identification and isolation of iron complexes in unusually high formal oxidation states, containing iron-oxygen or iron-nitrogen multiple bonds. The spectroscopic characterization and the reactivity studies of these model complexes provide vital insights into the mechanism that nature uses to induce the reductive cleavage of dioxygen or dinitrogen in carrying out a number of important biochemical oxidative transformations. Moreover, the comparative review of the electronic structures of the isoelectronic oxoiron and nitridoiron functionalities reveals that the Fe-N bonds are intrinsically more covalent than the Fe-O bonds.

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“…To our knowledge, only few tetradecanuclear Fe III clusters are known. These include triazole-bridged [Fe 14 O 6 (L) 6 (OMe) 18 Cl 6 ] clusters (where L = 1,2,3-triazole, benzotriazole, 5-methylbenzotriazole, 5,6-dimethylbenzotriazole, 5-chlorobenzotriazole) [22,27] with a {Fe 14 O 6 } core, an alkoxide-based [Bu 4 N] 2 [Fe 14 O 8 (OCH 2 Me) 20 Cl 8 ] [28] cluster and a oxo/peroxo pivalate-type [Fe 14 O 4 (O 2 ) 2 (Piv) 12 (L) 8 (H 2 O) 12 ](NO 3 ) 2 cage (where L = phosphonate ligand) [29] possessing a {Fe 14 O 8 } core, and finally a nitride (Et 4 N) 4 [Fe 14 N 8 (L)Cl 12 ] (where L = (Me 3 Sn) 3 N) cluster [30] with a {Fe 14 N 8 } core, yet no tetradecanuclear cluster with a {Fe 14 O 14 } core has been reported.…”

Section: Introductionmentioning

confidence: 99%