The Synthesis, Structure, and Reactivity of Phenyl Tris(3-tert-butylpyrazolyl)borato Iron Methyl, [PhTpBut]FeMe:  Isolation of a Four-Coordinate Monovalent Iron Carbonyl Complex, [PhTpBut]FeCO

Kisko, Jennifer L.; Hascall, Tony; Parkin, Gerard

doi:10.1021/ja982323p

Cited by 98 publications

(75 citation statements)

References 13 publications

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“…24 This comparison suggests that 2 likely contains high-spin Fe I centers, which is rare for a CO ligated iron center with tris(pyrazolyl)borate Fe I (CO) compounds as the only characterized examples. 16,27 Applying a magnetic field of 2 T at 4.8 K resulted in a slight line broadening for the doublet assigned to Fe( ii ), revealing an internal field of less than 4 T (Fig. S19†).…”

Section: Resultsmentioning

confidence: 99%

Reactivity of hydride bridges in a high-spin [Fe₃(μ-H)₃]³⁺ cluster: reversible H₂/CO exchange and Fe–H/B–F bond metathesis

et al. 2017

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Section: Resultsmentioning

confidence: 99%

Reactivity of hydride bridges in a high-spin [Fe₃(μ-H)₃]³⁺ cluster: reversible H₂/CO exchange and Fe–H/B–F bond metathesis

et al. 2017

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“…In his review of open-shell organometallic complexes, Poli notes that many decomposition pathways are invalidated by the absence of empty d-orbitals in high-spin complexes, 22 a contention supported by the analogous stability of Parkin's 14-electron methyliron complex (PhTptBu)-FeCH 3 . 27 Tris(pyrazolyl)borate and related ligands also lead to tetrahedral 15-electron cobalt(II)-methyl complexes. 28,29 The reactivity of paramagnetic methylnickel complexes is also relevant to nickel-containing enzymes.…”

Section: Discussionmentioning

confidence: 99%

Electronically Unsaturated Three-Coordinate Chloride and Methyl Complexes of Iron, Cobalt, and Nickel

et al. 2002

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Three-coordinate organometallic complexes are rare, especially with the prototypical methyl ligand. Using a hindered, rigid bidentate ligand (L), it is possible to create 12-electron methyliron(II) and 13-electron methylcobalt(II) complexes. These complexes are thermally stable, and 1 H NMR spectra suggest that the low coordination number is maintained in solution. Attempts to create the 14-electron LNiCH3 led instead to the three-coordinate nickel(I) complex LNi(THF). Single crystals of LMCH3 are isomorphous with the new three-coordinate chloride complexes LNiCl and LCoCl. Along with the recently reported LFeCl (Smith, J. M.; Lachicotte, R. J.; Holland, P. L. Chem. Commun. 2001, 1542), these are the only examples of threecoordinate iron(II), cobalt(II), and nickel(II) complexes with terminal chloride ligands, enabling the systematic evaluation of the effect of coordination number and metal identity on M-Cl bond lengths. Electronic structure calculations predict the ground states of the trigonal complexes.

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“…Bulky tris(pyrazolyl)borate ligands (Tp) have also been used to stabilise 14-electron tetracoordinated complexes, including TpFeCH3 (Scheme 11). 80,81 Another example of low electron count Fe(II)-methyl complex is square planar (IMes)2FeMe2 that was prepared by Glorius and collaborators by reacting Fe(N(SiMe3)2)2 with IMesCl (IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and treating the resulting (IMes)2FeCl2 with LiMe. The geometric change from the dichloride to the dimethyl complex was attributed by the authors to both the steric properties of the IMes ligands and the strong ligand field created by the -donor character of the carbene and the methyl ligands.…”

Section: Groupmentioning

confidence: 99%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, i.e. based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last 5 years. After a panoramic overview on M-CH3 compounds of groups 3 to 11 which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

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The Synthesis, Structure, and Reactivity of Phenyl Tris(3-tert-butylpyrazolyl)borato Iron Methyl, [PhTp^Bu^{^t}]FeMe: Isolation of a Four-Coordinate Monovalent Iron Carbonyl Complex, [PhTp^Bu^{^t}]FeCO

Cited by 98 publications

References 13 publications

Reactivity of hydride bridges in a high-spin [Fe₃(μ-H)₃]³⁺ cluster: reversible H₂/CO exchange and Fe–H/B–F bond metathesis

Reactivity of hydride bridges in a high-spin [Fe₃(μ-H)₃]³⁺ cluster: reversible H₂/CO exchange and Fe–H/B–F bond metathesis

Electronically Unsaturated Three-Coordinate Chloride and Methyl Complexes of Iron, Cobalt, and Nickel

Methyl Complexes of the Transition Metals

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The Synthesis, Structure, and Reactivity of Phenyl Tris(3-tert-butylpyrazolyl)borato Iron Methyl, [PhTpBut]FeMe: Isolation of a Four-Coordinate Monovalent Iron Carbonyl Complex, [PhTpBut]FeCO

Cited by 98 publications

References 13 publications

Reactivity of hydride bridges in a high-spin [Fe3(μ-H)3]3+ cluster: reversible H2/CO exchange and Fe–H/B–F bond metathesis

Reactivity of hydride bridges in a high-spin [Fe3(μ-H)3]3+ cluster: reversible H2/CO exchange and Fe–H/B–F bond metathesis

Electronically Unsaturated Three-Coordinate Chloride and Methyl Complexes of Iron, Cobalt, and Nickel

Methyl Complexes of the Transition Metals

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The Synthesis, Structure, and Reactivity of Phenyl Tris(3-tert-butylpyrazolyl)borato Iron Methyl, [PhTp^Bu^{^t}]FeMe: Isolation of a Four-Coordinate Monovalent Iron Carbonyl Complex, [PhTp^Bu^{^t}]FeCO

Reactivity of hydride bridges in a high-spin [Fe₃(μ-H)₃]³⁺ cluster: reversible H₂/CO exchange and Fe–H/B–F bond metathesis

Reactivity of hydride bridges in a high-spin [Fe₃(μ-H)₃]³⁺ cluster: reversible H₂/CO exchange and Fe–H/B–F bond metathesis