Synthesis of bis[bis(trimethylsilyl)amido]iron(II). Structure and bonding in M[N(SiMe3)2]2 (M = manganese, iron, cobalt): two-coordinate transition-metal amides

Andersen, Richard A.; Fægri, Knut; Green, Jennifer C.; Haaland, Arne; Läppert, Michael F.; Leung, Wing Por; Rypdal, Kristin

doi:10.1021/ic00283a022

Cited by 308 publications

(280 citation statements)

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“…If, on the other hand, electron transfer occurs first, then the oneelectron reduction of dad would reduce the energy gap between the t 2g and e g sets of d orbitals and induce the [16] (1.694 g, 4.498 mmol) dissolved in dme (15 mL) was slowly added to a solution of H 2 pda (1.800 g, 4.089 mmol) in dme (15 mL) at À80 8C. The reaction mixture was allowed to warm to room temperature and was stirred for an additional 1 h. The reaction volume was decreased to 15 mL by evaporation in vacuo, and hexane (ca.…”

Section: Methodsmentioning

confidence: 99%

Reversible Electron Transfer Coupled to Spin Crossover in an Iron Coordination Salt in the Solid State

et al. 2008

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Mössbauer spectroscopy of a series of bis(a-diimine)iron complexes has recently unequivocally shown that these distorted tetrahedral complexes with a triplet ground state contain a high-spin ferrous ion (S Fe = 2) and two monoanionic p radicals LC À (S rad = 1/2, Scheme 1), which are intramolecularly antiferromagnetically coupled to the iron ion to yield the observed S t = 1 ground state.[1] The electronic structure of these complexes cannot be described as species containing a low-valent iron(0) center (S Fe = 1, d 8 ) and two neutral adiimine ligands as proposed [2] in the literature. This [1] and other [3, 4] recent studies have clearly established that adiimines are noninnocent ligands with three accessible oxidation levels L 0 , LC À , and L 2À, which can be clearly discerned by their differing CÀC and CÀN bond lengths (Scheme 1).In an attempt to synthesize such [FeL 2 ] complexes with two different a-diimines (heteroleptic complexes), we prepared the extremely air-sensitive complex [Fe II (pda 2À )(dme) 2 ] (1; pda 2À = N,N'-bis(pentafluorophenyl)-o-phenylenediamido(2À) ligand, dme = dimethoxyethane). When 1 reacted with 1 equivalent of N,N'-bis(phenyl)-2,3-dimethyl-1,4-diaza-1,3-butadiene (dad 0 ), the EI mass spectrum indicated the presence of [Fe(pda)(dad)], but the isolated main product turned out to be black crystals of [Fe(dad) 3 ][Fe(pda) 2 ]·-(toluene) (2; Figure 1). When the ratio dad:1 was changed to 3:2, the yield of 2 increased to 43 %. As complex 2 possesses a very interesting temperature-dependent electronic structure (see below), its molecular structure was determined by singlecrystal X-ray crystallography at 120 and 270 K.[5]The low-temperature structure of 2 consists of a cationanion pair (Figure 2). Both the octahedral cation and the distorted tetrahedral anion contain one central iron ion; the charges of these ions are not specified at this point, because both dad and pda are noninnocent ligands. As shown in Scheme 1, their respective oxidation level can be determined by X-ray crystallography. The three dad ligands in 2 have long CÀC bonds (av 1.473(4) ) and short CÀN bonds (av [*] Dr.

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Section: Methodsmentioning

confidence: 99%

Reversible Electron Transfer Coupled to Spin Crossover in an Iron Coordination Salt in the Solid State

et al. 2008

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“…N HMDS -dipyridylamine were purchased from Sigma Aldrich and used as received. Fe(HMDS)2 was prepared according to a modified literature procedure from Lappert et al 48,86 Hexane was dried prior to synthesis by Grubbs column (PureSolv micro solvent purification system, Innovative Technologies) to remove any traces of moisture and dissolved oxygen and stored over 4 Å molecular sieves. Toluene and THF were used immediately after being freshly distilled over sodium benzophenone ketyl under nitrogen.…”

Section: Experimental General Conditionsmentioning

confidence: 99%

Synthetic, structural and magnetic implications of introducing 2,2′-dipyridylamide to sodium-ferrate complexes

et al. 2017

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This version is available at https://strathprints.strath.ac.uk/60604/ Strathprints is designed to allow users to access the research output of the University of Strathclyde. Unless otherwise explicitly stated on the manuscript, Copyright © and Moral Rights for the papers on this site are retained by the individual authors and/or other copyright owners. Please check the manuscript for details of any other licences that may have been applied. You may not engage in further distribution of the material for any profitmaking activities or any commercial gain. You may freely distribute both the url (https://strathprints.strath.ac.uk/) and the content of this paper for research or private study, educational, or not-for-profit purposes without prior permission or charge.Any correspondence concerning this service should be sent to the Strathprints administrator: strathprints@strath.ac.ukThe Strathprints institutional repository (https://strathprints.strath.ac.uk) is a digital archive of University of Strathclyde research outputs. It has been developed to disseminate open access research outputs, expose data about those outputs, and enable the management and persistent access to Strathclyde's intellectual output. Using a transamination approach to access novel Fe(II) complexes, this study presents the synthesis, X-ray crystallographic and magnetic characterisation of a series of new iron complexes containing the multifunctional 2,2-dipyridylamide (DPA) ligand using iron bis(amide) [{Fe(HMDS)2}2] and sodium ferrate [{NaFe(HMDS)3} ] (1) as precursors (HMDS = 1,1,1,3,3,3hexamethyldisilazide). Reactions of DPA(H) with 1 show exceptionally good stoichiometric control, allowing access to heteroleptic [(THF)2·NaFe(DPA)(HMDS)2] (3) and homoleptic [{THF·NaFe(DPA)3} ] (4) by using 1 and 3 equivalents of DPA(H) respectively. Linking this methodology and co-complexation, which is a more widely used approach to prepare heterobimetallic complexes, 3 can also be prepared by combining NaHMDS with heteroleptic [{Fe(DPA)(HMDS)}2] (2). In turn, 2 has been also synthesised and structurally defined by reacting [{Fe(HMDS)2}2] with two equivalents of DPA(H). Structural studies demonstrate the coordination flexibility of the N-bridged bis(heterocycle) ligand DPA, with 2 and 3 exhibiting discrete monomeric motifs, whereas 4 displays a much more intricate supramolecular structure, with one of its DPA ligands coordinating in an anti/anti fashion (as opposed to 2 and 3 where DPA shows a syn/syn conformation), which facilitates propagation of the structure via its central amido N. Magnetic studies confirmed the high-spin electron configuration of the iron(II) centres in all three compounds and revealed the existence of weak ferromagnetic interactions in dinuclear compound 2 (J = 1.01 cm -1 ). Journal Name ARTICLE

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“…So konnten z. B. monomer aufgebaute Ûbergangsmetallverbindungen mit der extrem niedrigen Koordinationszahl 2 erhalten werden [3]. Wir benutzten Rb-und CsN(SiMe 3 ) 2 zur Synthese von metallorganischen Verbindungen des Rubidiums und Caesiums, indem wir mit den Hexamethyldisilaziden die C±H-aciden Kohlenwasserstoffe Cyclopentadien, Inden und Fluoren deprotonierten [4].…”

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Kristall- und Molekülstruktur der solvatfreien Hexamethyldisilazide des Rubidiums und Caesiums und die Kristallstruktur eines Toluolsolvates

Neander

Behrens

1999

Z. anorg. allg. Chem.

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Die Kristallstrukturen der dimeren Rubidium‐ und Caesium‐hexamethyldisilazide [MN(SiMe3)2]2 werden beschrieben. [RbN(SiMe3)2]2 (1) kristallisiert in der monoklinen Raumgruppe P21/c mit a = 1044.7(2), b = 891.1(2), c = 1281.0(3) pm, β = 100.26(2)°, Z = 2. [CsN(SiMe3)2]2 (2) kristallisiert in der orthorhombischen Raumgruppe Pbca mit a = 1270.81(2), b = 1281.16(1), c = 1539.65(2) pm, Z = 4. Beide Verbindungen enthalten einen viergliedrigen [M–N–]2‐Ring, der auf einem Inversionszentrum liegt. Die M–N‐Bindungslängen betragen: 287.8(2), 295.6(2) pm (1) und 307.4(2), 314.9 (2) pm (2). Das Solvat [CsN(SiMe3)2]2 · C7H8 (3) kristallisiert aus Toluol in der triklinen Raumgruppe P1 mit a = 854.00(2), b = 979.58(2), c = 1084.45(3) pm, α = 111.482(1), β = 93.821(1), γ = 108.546(1)°, Z = 1. In dieser Verbindung bilden dimere Einheiten [CsN(SiMe3)2]2 und Toluolmoleküle eine polymere Kette.

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Synthesis of bis[bis(trimethylsilyl)amido]iron(II). Structure and bonding in M[N(SiMe3)2]2 (M = manganese, iron, cobalt): two-coordinate transition-metal amides

Cited by 308 publications

References 2 publications

Reversible Electron Transfer Coupled to Spin Crossover in an Iron Coordination Salt in the Solid State

Reversible Electron Transfer Coupled to Spin Crossover in an Iron Coordination Salt in the Solid State

Synthetic, structural and magnetic implications of introducing 2,2′-dipyridylamide to sodium-ferrate complexes

Kristall- und Molekülstruktur der solvatfreien Hexamethyldisilazide des Rubidiums und Caesiums und die Kristallstruktur eines Toluolsolvates

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