Cationic low-spin bis[1,2-bis(dialkylphosphino)ethane]iron(II) complexes

Bellerby, John M.; Mays, Martin J.; Sears, Paul L.

doi:10.1039/dt9760001232

Cited by 28 publications

(18 citation statements)

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“…This also applies to the corresponding dppe system [FeH(N 2 )(dppe) 2 ] + ( 1b ), which even forms in THF by reaction of the five‐coordinate precursor [FeH(dppe) 2 ]BPh 4 with air 58, 59. The five‐coordinate complex [FeCl(depe) 2 ] + , in contrast, is extremely oxygen sensitive in solution 64. These remarkable differences in reactivity are correlated with different electronic ground states that we have determined by a combination of magnetic susceptibility measurements, various spectroscopic methods, and DFT calculations.…”

Section: End‐on Terminal Coordinationmentioning

confidence: 98%

Theoretical, spectroscopic, and mechanistic studies on transition‐metal dinitrogen complexes: Implications to reactivity and relevance to the nitrogenase problem

2006

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Dinitrogen complexes of transition metals exhibit different binding geometries of N2 (end-on terminal, end-on bridging, side-on bridging, side-on end-on bridging), which are investigated by spectroscopy and DFT calculations, analyzing their electronic structure and reactivity. For comparison, a bis(mu-nitrido) complex, where the N--N bond has been split, has been studied as well. Most of these systems are highly covalent, and have strong metal-nitrogen bonds. In the present review, particular emphasis is put on a consideration of the activation of the coordinated dinitrogen ligand, making it susceptible to protonation, reactions with electrophiles or cleavage. In this context, theoretical, structural, and spectroscopic data giving informations on the amount of charge on the N2 unit are presented. The orbital interactions leading to a charge transfer from the metals to the dinitrogen ligand and the charge distribution within the coordinated N2 group are analyzed. Correlations between the binding mode and the observed reactivity of N2 are discussed.

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Section: End‐on Terminal Coordinationmentioning

confidence: 98%

Theoretical, spectroscopic, and mechanistic studies on transition‐metal dinitrogen complexes: Implications to reactivity and relevance to the nitrogenase problem

2006

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“…The synthesis of [FeCl(N 2 )(depe) 2 ](BPh 4 ) (2) has been performed according to a procedure modified from the literature [13,15] a) The missing coordinates are generated by reflections.…”

Section: Sample Preparation and Isotopic Substitutionmentioning

confidence: 99%

“…Thus, the complex [FeH(dppe) 2 ] ϩ in a THF solution or in the solid state picks up N 2 from air, leading to [FeH(N 2 )(dppe) 2 ] ϩ [13,14]. A methanolic solution of [FeCl(depe) 2 ] ϩ , on the other hand, is extremely sensitive towards oxidation [13,15]. In order to understand these drastic differences in reactivity between otherwise identical hydrido and halogeno complexes, we started an investigation of the five-coordinate fragments [FeX(depe) 2 ] ϩ , Xϭhalide and hydride, by X-ray crystallography and spectroscopy (UV/Vis absorption, Mössbauer).…”

Section: Introductionmentioning

confidence: 99%

Vibrational Properties of [FeH(N2)(depe)2]+ and [FeCl(N2)(depe)2]+]: Dinitrogen Bonding in the Low Activation Limit

Franke

Wiesler

Lehnert

et al. 2002

Z. anorg. allg. Chem.

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“…Our experiments showed that two equivalents of the larger diphosphine dcpe cannot bind to FeCl2 to form "FeCl2(dcpe)2" presumably because they create too much steric crowding around the metal center (formation of complexes of the type FeCl2(L)2 has been previously shown for smaller ligands L = dmpe and depe). 13 Even with heating, the only product from the reaction of FeCl2 and two or more equivalents of dcpe is the known species FeCl2(dcpe). 14 Nonetheless, we found that the reaction of paramagnetic FeCl2(dcpe) with two equivalents of NaBEt3H and one additional equivalent dcpe successfully yielded the diamagnetic, bis-ligated species cis-FeH2(dcpe)2 (1) as a pale yellow powder in 59% yield (Scheme 2).…”

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confidence: 99%

Synthesis and reactivity of cis-FeH2(dcpe)2 (dcpe = 1,2-bis(dicyclohexylphosphino)ethane)

Summerscales

Scott

Viswanathan

et al. 2016

Inorganic Chemistry Communications

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A new six-coordinate iron dihydride cis-FeH2(dcpe)2 (1) has been synthesized (dcpe = 1,2-bis(dicyclohexylphosphino)ethane). It has been found to react with either 1,4cyclohexadiene or tert-butylethylene in toluene to give the respected hydrogenated hydrocarbon and the zerovalent species Fe(dcpe)(toluene) (2). When this reaction with acceptor olefins was performed in methylcyclohexane, transfer dehydrogenation was observed to give low-yields of iron-bound toluene in 2. ______________________________________________________________________________ Selective C-H activation and functionalization of alkanes continues to be a longstanding challenge for chemists. 1 This is despite demand from industry to develop more effective methods for transforming simple hydrocarbons such as methane into liquid fuels or basic building blocks for pharmaceutical synthesis. Single-site, molecular species, e.g. organometallic and transition metal coordination compounds, have shown some remarkably selective activities towards the breaking of C-H bonds in hydrocarbons, and in a few cases, methane, at ambient temperatures and pressures. 2-4 Notably, the iron complex FeH2(dmpe)2 (dmpe = 1,2-bis(dimethylphosphino)ethane) has been shown to C-H activate a variety of alkanesincluding methane via a photolytic method in liquid xenon at-100°C, presumably via the transient zerovalent Fe(dmpe)2 species (Scheme 1). 5-8 Roddick et al. demonstrated that a thermolytic method could be used to effect aliphatic C-H activation for similar

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Cationic low-spin bis[1,2-bis(dialkylphosphino)ethane]iron(II) complexes

Abstract: Cationic Low-spin Bis[l,2-bis(dial kylphosphino)ethane] iron(ir) Complexes tBy J o h n M.

Cited by 28 publications

References 0 publications

Theoretical, spectroscopic, and mechanistic studies on transition‐metal dinitrogen complexes: Implications to reactivity and relevance to the nitrogenase problem

Theoretical, spectroscopic, and mechanistic studies on transition‐metal dinitrogen complexes: Implications to reactivity and relevance to the nitrogenase problem

Vibrational Properties of [FeH(N2)(depe)2]+ and [FeCl(N2)(depe)2]+]: Dinitrogen Bonding in the Low Activation Limit

Synthesis and reactivity of cis-FeH2(dcpe)2 (dcpe = 1,2-bis(dicyclohexylphosphino)ethane)

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