Mono- and binuclear σ-aryl iron-lithium hydrides; synthesis and molecular structure

Bazhenova, T. A.; Kachapina, L. M.; Шилов, А. Е.; Antipin, M. Yu.; Struchkov, Yu. T.

doi:10.1016/0022-328x(92)83223-5

Cited by 27 publications

(14 citation statements)

References 3 publications

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“…The structure reported for [FePh 4 ] 4À seems to have a severe scissoring distortion (C-Fe-C bond angles of 618), [120] but later structural redeterminations [121,122] of that compound found the Fe atom to be hexacoordinate with regular bond angles of 908, corresponding to the formula [FeH 2 Ph 4 ] 4À . Although statistically of little significance, a few sawhorse structures have beeen identified, such as the Ir I and Ru 0 compounds presented in Table 2.…”

Section: Distribution Of Experimental Tetracoordinate Structuresmentioning

confidence: 92%

Mapping the Stereochemistry and Symmetry of Tetracoordinate Transition‐Metal Complexes

Cirera

Alemany

Álvarez

2003

Chemistry A European J

198

203

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A continuous shape and symmetry study of tetracoordinate transition-metal complexes is presented, in an attempt to provide a systematic description of the stereochemistry of the metal coordination sphere in this important family of compounds. A tetrahedron/square-planar symmetry map has been developed, the main distortion paths of the ideal geometries are presented, and the applicability of a sawhorse shape measure is discussed. More than 13,000 structural data sets have been analyzed and the corresponding stereochemistries assigned from the values of their tetrahedral and square-planar symmetry measures. A good number of structures that are quite distant from the two ideal geometries can be adequately described as snapshots along the spread pathway for their interconversion, making use of the corresponding path deviation function. Further analysis of the structural data by metal electron configuration or by the denticity and conformation of the ligands provide general rules to describe the stereochemical preferences of tetracoordinate transition metal centers.

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Section: Distribution Of Experimental Tetracoordinate Structuresmentioning

confidence: 92%

Mapping the Stereochemistry and Symmetry of Tetracoordinate Transition‐Metal Complexes

Cirera

Alemany

Álvarez

2003

Chemistry A European J

198

203

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“…1,2 Organoferrates devoid of stabilizing ligands (nonstabilized organoferrates) are scarce. 2 Reported examples include tetramethylferrate (1; 3 Scheme 1) and tetrabenzylferrate(III) (2), 4 [Fe(Mes) 3 ] − (3a) 5 and [FeBn 3 ] − (3b), 4 tetramethyl-and tetraphenyliron(II) complexes 4 and 5, 2 the tetraphenyl dihydride complex 6, 6 the Fe(0) complex 7, 7 formally Fe(−II) complexes 8 and 9, 8 and the octanuclear ferrate [MgCl(thf) 5 ][Fe 8 Me 12 ]. 9 With the exception of 1, 2, and 3a,b, these complexes often contain either direct Fe−metal (most often Fe−Li) interactions or solvated metal cation(s) (most often lithium) in the proximity of the iron center.…”

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confidence: 99%

“…The Fe−C(η 1 -Ph) distance (1.971−1.977 Å; see the Supporting Information) in complex 11 is slightly shorter than its counterpart in 5 (2.084−2.216 Å) 2 and 6 (2.056 Å). 6 The distance between the Fe(I) center and the η 6 -phenyl ring (1.578 Å) is in line with the values reported for (η-arene)(Cp)Fe II complexes. 12,13 It is remarkable that, despite the presence of lithium ion and diethyl ether in the reaction mixture, neither is present in complex 11.…”

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confidence: 99%

A Monometallic Iron(I) Organoferrate

Zhurkin

Wodrich

2017

Organometallics

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“…However, there have been various dilithio μ 3 -hydride compounds reported with other metals such as Ga, 168,169 Al, 166,170−173 Zr, 174−176 W, 177,178 Sm, 179,180 Ta, 178 and Fe. 181 …”

Section: Resultsmentioning

confidence: 99%

Main Group Multiple C–H/N–H Bond Activation of a Diamine and Isolation of A Molecular Dilithium Zincate Hydride: Experimental and DFT Evidence for Alkali Metal–Zinc Synergistic Effects

et al. 2011

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The surprising transformation of the saturated diamine (iPr)NHCH2CH2NH(iPr) to the unsaturated diazaethene [(iPr)NCH=CHN(iPr)]2- via the synergic mixture nBuM, (tBu)2Zn and TMEDA (where M = Li, Na; TMEDA = N,N,N′,N′-tetramethylethylenediamine) has been investigated by multinuclear NMR spectroscopic studies and DFT calculations. Several pertinent intermediary and related compounds (TMEDA)Li[(iPr)NCH2CH2NH(iPr)]Zn(tBu)2 (3), (TMEDA)Li[(iPr)NCH2CH2CH2N(iPr)]Zn(tBu) (5), {(THF)Li[(iPr)NCH2CH2N(iPr)]Zn(tBu)}2 (6), and {(TMEDA)Na[(iPr)NCH2CH2N(iPr)]Zn(tBu)}2 (11), characterized by single-crystal X-ray diffraction, are discussed in relation to their role in the formation of (TMEDA)M[(iPr)NCH=CHN(iPr)]Zn(tBu) (M = Li, 1; Na, 10). In addition, the dilithio zincate molecular hydride [(TMEDA)Li]2[(iPr)NCH2CH2N(iPr)]Zn(tBu)H 7 has been synthesized from the reaction of (TMEDA)Li[(iPr)NCH2CH2NH(iPr)]Zn(tBu)23 with nBuLi(TMEDA) and also characterized by both X-ray crystallographic and NMR spectroscopic studies. The retention of the Li–H bond of 7 in solution was confirmed by 7Li–1H HSQC experiments. Also, the 7Li NMR spectrum of 7 in C6D6 solution allowed for the rare observation of a scalar 1JLi–H coupling constant of 13.3 Hz. Possible mechanisms for the transformation from diamine to diazaethene, a process involving the formal breakage of four bonds, have been determined computationally using density functional theory. The dominant mechanism, starting from (TMEDA)Li[(iPr)NCH2CH2N(iPr)]Zn(tBu) (4), involves the formation of a hydride intermediate and leads directly to the observed diazaethene product. In addition the existence of 7 in equilibrium with 4 through the dynamic association and dissociation of a (TMEDA)LiH ligand, also provides a secondary mechanism for the formation of the diazaethene. The two reaction pathways (i.e., starting from 4 or 7) are quite distinct and provide excellent examples in which the two distinct metals in the system are able to interact synergically to catalyze this otherwise challenging transformation.

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Mono- and binuclear σ-aryl iron-lithium hydrides; synthesis and molecular structure

Cited by 27 publications

References 3 publications

Mapping the Stereochemistry and Symmetry of Tetracoordinate Transition‐Metal Complexes

Mapping the Stereochemistry and Symmetry of Tetracoordinate Transition‐Metal Complexes

A Monometallic Iron(I) Organoferrate

Main Group Multiple C–H/N–H Bond Activation of a Diamine and Isolation of A Molecular Dilithium Zincate Hydride: Experimental and DFT Evidence for Alkali Metal–Zinc Synergistic Effects

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