Transition metal complexes with sulfur ligands. Part CLV.11For Part CLIV see Ref. [1], Eur. J. Inorg. Chem., in press. Structural and spectroscopic characterization of hydrogen bridge diastereomers of [μ-N2H2{Fe(PR3)(‘tpS4’)}2] diazene complexes (‘tpS4’2−=1,2-bis(2-mercaptophenylthio)phenylene(2−))

Sellmann, Dieter; Blum, D.; Heinemann, Frank W.

doi:10.1016/s0020-1693(02)00987-8

Cited by 30 publications

(13 citation statements)

References 37 publications

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“…Using a variety of iron sulfur scaffolds, Sellmann et al successfully synthesized a number of bridging Á 1 diazene complexes [102][103][104][105]. Starting with the iron hydrazine complex shown in Eq.…”

Section: Methodsmentioning

confidence: 99%

Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Crossland

Tyler

2010

Coordination Chemistry Reviews

224

216

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Section: Methodsmentioning

confidence: 99%

Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Crossland

Tyler

2010

Coordination Chemistry Reviews

224

216

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“…Structural determination of 102 revealed that the diazene moiety forms N–H···S(thiolate) hydrogen bonding networks, as suggested from the H···S distances of 2.201 and 2.780 Å. Direct trapping of diazene, which is generated in situ from thermolysis of PhSO 2 N 2 H 3 or acidification of K 2 N 2 (CO 2 ) 2 , is possible with analogous Fe complexes carrying different S-based supporting ligands, [Fe(P n Pr 3 )(“S 4 ”)] (“S 4 ” = 1,2-bis(2-sulfanylphenylthio)ethane dianion) , and [Fe(PR 3 )(“tpS 4 ”)] (R = n Pr, n Bu; “tpS 4 ” = 1,2-bis(2-mercaptophenylthio)phenylene dianion) (Scheme b) . The resultant Fe-diazene complexes [{Fe(P n Pr 3 )(“S 4 ”)} 2 (μ-N 2 H 2 )] ( 103 ) and [{Fe(PR 3 )(“tpS 4 ”)} 2 (μ-N 2 H 2 )] (R = n Pr ( 104 ), n Bu) also contain bridging trans -N 2 H 2 and exhibit N–N bond distances comparable among this class of complexes, e.g.…”

Section: Sulfur-supported Transition Metal Complexes In N2 Chemistrymentioning

confidence: 99%

Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry

2020

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Transition metal–sulfur (M–S) compounds are an indispensable means for biological systems to convert N2 into NH3 (biological N2 fixation), and these may have emerged by chemical evolution from a prebiotic N2 fixation system. With a main focus on synthetic species, this article provides a comprehensive review of the chemistry of M–S compounds related to the conversion of N2 and the structures/functions of the nitrogenase cofactors. Three classes of M–S compounds are highlighted here: multinuclear M–S clusters structurally or functionally relevant to the nitrogenase cofactors, mono- and dinuclear transition metal complexes supported by sulfur-containing ligands in N2 and N2H x (x = 2, 4) chemistry, and metal sulfide-based solid materials employed in the reduction of N2. Fair assessments on these classes of compounds revealed that our understanding is still limited in N2 reduction and related substrate reductions. Our aims of this review are to compile a collection of studies performed at atomic to mesoscopic scales and to present potential opportunities for elucidating the roles of metal and sulfur atoms in the biological N2 fixation that might be helpful for the development of functional materials.

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“…Known transition metal diazene complexes reveal a range of N 2 H 2 coordination motifs (Figure ). − Since the lifetime of free diazene is so short in solution (aqueous N 2 H 2 decay: k = 2.2 × 10 4 M –1 s –1 at 25 °C), isolable metal-diazene complexes enable the study of N 2 H 2 and the effects of coordination at metal centers by a wide variety of spectroscopic and other direct methods. − …”

Section: Introductionmentioning

confidence: 99%

“…Recent exploration of dynamic secondary coordination sphere Lewis acid and H-bonding interactions include metal-N 2 (Figure a) − and metal-N 2 H 4 (Figure c) complexes that accent studies by Sellmann and co-workers which outline secondary coordination sphere H-bonding with N 2 H 2 ligands (Figure b). − Guided by a developing understanding of the nitrogenase FeMo-cofactor, Sellmann’s complexes modeled possible cluster sulfur–N 2 H 2 H-bonding interactions . These complexes, typically hosting Ru or Fe centers, possess “bifurcated” H-bonding whereby the N 2 H 2 ligand simultaneously engages in a short and long H-bonding interaction with proximal S-donors (Figure b).…”

Section: Introductionmentioning

confidence: 99%

Uncovering Redox Non-innocent Hydrogen-Bonding in Cu(I)-Diazene Complexes

et al. 2021

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The life-sustaining reduction of N2 to NH3 is thermoneutral yet kinetically challenged by high-energy intermediates such as N2H2. Exploring intramolecular H-bonding as a potential strategy to stabilize diazene intermediates, we employ a series of [ xHetTpCu]2(μ-N2H2) complexes that exhibit H-bonding between pendant aromatic N-heterocycles (xHet) such as pyridine and a bridging trans-N2H2 ligand at copper(I) centers. X-ray crystallography and IR spectroscopy clearly reveal H-bonding in [pyMeTpCu]2(μ-N2H2) while low-temperature 1H NMR studies coupled with DFT analysis reveals a dynamic equilibrium between two closely related, symmetric H-bonded structural motifs. Importantly, the xHet pendant negligibly influences the electronic structure of xHetTpCuI centers in xHetTpCu(CNAr2,6‑Me2 ) complexes that lack H-bonding as judged by nearly indistinguishable ν(CN) frequencies (2113–2117 cm–1). Nonetheless, H-bonding in the corresponding [ xHetTpCu]2(μ-N2H2) complexes results in marked changes in ν(NN) (1398–1419 cm–1) revealed through resonance Raman studies. Due to the closely matched N–H BDEs of N2H2 and the pyH0 cation radical, the aromatic N-heterocyclic pendants may encourage partial H-atom transfer (HAT) from N2H2 to xHet through redox-non-innocent H-bonding in [ xHetTpCu]2(μ-N2H2). DFT studies reveal modest thermodynamic barriers for concerted transfer of both H-atoms of coordinated N2H2 to the xHet pendants to generate tautomeric [ xHetHTpCu]2(μ-N2) complexes, identifying metal-assisted concerted dual HAT as a thermodynamically favorable pathway for N2/N2H2 interconversion.

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Cited by 30 publications

References 37 publications

Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry

Uncovering Redox Non-innocent Hydrogen-Bonding in Cu(I)-Diazene Complexes

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Cited by 30 publications

References 37 publications

Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Iron–dinitrogen coordination chemistry: Dinitrogen activation and reactivity

Metal–Sulfur Compounds in N2 Reduction and Nitrogenase-Related Chemistry

Uncovering Redox Non-innocent Hydrogen-Bonding in Cu(I)-Diazene Complexes

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Metal–Sulfur Compounds in N₂ Reduction and Nitrogenase-Related Chemistry