Synthesis and reactivity of iron(II) hydride complexes containing diphenylphosphine ligands

Maser, Leon; Flosdorf, Kimon; Langer, Róbert

doi:10.1016/j.jorganchem.2015.04.030

Cited by 5 publications

(2 citation statements)

References 76 publications

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“…This behavior contrasts significantly with that of H 2 Fe(CO) 4 , which liberates dihydrogen above −10 °C. Iron dihydrides of the type H 2 Fe(PR 3 ) 4 and H 2 Fe(CO) 2 (PR 3 ) 2 have been crystallographically characterized; however, an important distinction is that they are derived from hydride and proton sources and not H 2 . − …”

Section: Resultsmentioning

confidence: 99%

Probing for Four-Coordinate Zerovalent Iron in a π-Acidic Ligand Field: A Functional Source of FeL₄ Enabled by Labile Dinitrogen Binding

et al. 2020

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It has long been recognized that the first intermediate in chemical reactions mediated by Fe(CO)5 is Fe(CO)4. However, the extreme instability of this unsaturated, high-spin species has hampered detailed structural and stoichiometric reactivity studies. The previously reported heteroleptic complex Fe(N2)(CO)2(CNArTripp2)2 (ArTripp2 = 2,6-(2,4,6-(i-Pr)3C6H2)2C6H3), which is isolobal to Fe(CO)5, is shown here to possess a labile dinitrogen ligand that allows it to perform reactions analogous to Fe(CO)4. Specifically, Fe(N2)(CO)2(CNArTripp2)2 oxidatively adds dihydrogen, white phosphorus, and the Si–H bonds of triethylsilane and phenylsilane readily at room temperature and also binds tetrahydrofuran in the absence of N2. Accordingly, Fe(N2)(CO)2(CNArTripp2)2 effectively serves as a masked form of Fe(CO)4, allowing for well-defined reactivity and structurally characterizable reaction products.

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Section: Resultsmentioning

confidence: 99%

Probing for Four-Coordinate Zerovalent Iron in a π-Acidic Ligand Field: A Functional Source of FeL₄ Enabled by Labile Dinitrogen Binding

et al. 2020

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“…Despite being known to form salts with alkali metals with different substituents attached to phosphorus since at least the 1960s, 1 − 11 and likely as early as 1940, 12 the coordinative properties of phosphinodiboranates with different metals have only emerged recently. 13 In 2018, we showed that M(H 3 BP t Bu 2 BH 3 ) 3 (M- t Bu), where M = uranium or a lanthanide, can be prepared by salt metathesis reactions using trivalent f-metal iodides and K(H 3 BP t Bu 2 BH 3 ) ( Scheme 2 a). 14 Later, in 2021, Morris et al reported the first magnesium complex containing Ph-PDB.…”

Section: Introductionmentioning

confidence: 99%

The Influence of Phosphorus Substituents on the Structures and Solution Speciation of Trivalent Uranium and Lanthanide Phosphinodiboranates

Zgrabik,

Bhowmick,

Eckstrom

et al. 2023

Inorg. Chem.

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Here, we report the mechanochemical synthesis and characterization of homoleptic uranium and lanthanide phosphinodiboranates with isopropyl and ethyl substituents attached to phosphorus. M(H 3 BP i Pr 2 BH 3 ) 3 complexes with M = U, Nd, Sm, Tb, and Er were prepared by ball milling UI 3 (THF) 4 , SmBr 3 , or MI 3 with three equivalents of K(H 3 BP i Pr 2 BH 3 ). M(H 3 BPEt 2 BH 3 ) 3 with M = U and Nd were prepared similarly using K(H 3 BPEt 2 BH 3 ), and the complexes were purified by extraction and crystallization from Et 2 O or CH 2 Cl 2 . Single-crystal XRD studies revealed that all five M(H 3 BP i Pr 2 BH 3 ) 3 crystallize as dimers, despite the significant differences in metal radii across the series. In contrast, Nd(H 3 BPEt 2 BH 3 ) 3 with smaller ethyl substituents crystallized as a coordination polymer. Crystals of U(H 3 BPEt 2 BH 3 ) 3 were not suitable for structural analysis, but crystals of U(H 3 BPMe 2 BH 3 ) 3 isolated in low yield by solution methods were isostructural with Nd(H 3 BPEt 2 BH 3 ) 3 . 1 H and 11 B NMR studies in C 6 D 6 revealed that all of the complexes form mixtures of monomer and oligomers when dissolved, and the extent of oligomerization was highly dependent on metal radius and phosphorus substituent size. A comprehensive analysis of all structurally characterized uranium and lanthanide phosphinodiboranate complexes reported to date, including those with larger Ph and t Bu substituents, revealed that the degree of oligomerization in solution can be correlated to differences in B−P−B angles obtained from single-crystal XRD studies. Density functional theory calculations, which included structural optimizations in combination with conformational searches using tight binding methods, replicated the general experimental trends and revealed free energy differences that account for the different solution and solid-state structures. Collectively, these results reveal how steric changes to phosphorus substituents significantly removed from metal coordination sites can have a significant influence on solution speciation, deoligomerization energies, and the solid-state structure of homoleptic phosphinodiboranate complexes containing trivalent f-metals.

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An iron(ii) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity

et al. 2016

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After lithiation of PYR-H2 (PYR = [(HCCMeNC6H3(iPr)2)2(C5H5-N)]2−) – the precursor of an expanded β-diketiminato ligand system with two binding pockets – with KN(TMS)2 the reaction of the resulting potassium salt with FeBr2 led to a dinuclear iron(II) bromide complex [(PYR)Fe(μ-Br)2Fe] (1). Through treatment with KHBEt3 the bromide ligands could be replaced by hydrides to yield [PYR)Fe2(μ-H)2] (2), a distorted analogue of known β-diketiminato iron hydride complexes, as evidenced by NMR, Mößbauer and X-ray absorption spectroscopy, as well as by its reactivity: For instance, 2 reacts with the proton source lutidinium triflate via protonation of the hydride ligands to form an iron(II) product [(PYR)Fe2(OTf)2] (4), while CO2 inserts into the Fe-H bonds generating the formate complex [(PYR)Fe2(μ-HCOO)2] (5); in the presence of traces of water partial hydrolysis occurs so that [(PYR)Fe2(μ-OH)(μ-HCOO)] (6) is isolated. Altogether, the iron(II) chemistry supported by the PYR2− ligand is distinctly different from the one of nickel(II), where both, the arrangement of the two binding pockets and the additional pyridyl donor led to diverging features as compared with the corresponding system based on the parent β-diketiminato ligand.

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Synthesis and reactivity of iron(II) hydride complexes containing diphenylphosphine ligands

Cited by 5 publications

References 76 publications

Probing for Four-Coordinate Zerovalent Iron in a π-Acidic Ligand Field: A Functional Source of FeL₄ Enabled by Labile Dinitrogen Binding

Probing for Four-Coordinate Zerovalent Iron in a π-Acidic Ligand Field: A Functional Source of FeL₄ Enabled by Labile Dinitrogen Binding

The Influence of Phosphorus Substituents on the Structures and Solution Speciation of Trivalent Uranium and Lanthanide Phosphinodiboranates

An iron(ii) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity

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Synthesis and reactivity of iron(II) hydride complexes containing diphenylphosphine ligands

Cited by 5 publications

References 76 publications

Probing for Four-Coordinate Zerovalent Iron in a π-Acidic Ligand Field: A Functional Source of FeL4 Enabled by Labile Dinitrogen Binding

Probing for Four-Coordinate Zerovalent Iron in a π-Acidic Ligand Field: A Functional Source of FeL4 Enabled by Labile Dinitrogen Binding

The Influence of Phosphorus Substituents on the Structures and Solution Speciation of Trivalent Uranium and Lanthanide Phosphinodiboranates

An iron(ii) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity

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Probing for Four-Coordinate Zerovalent Iron in a π-Acidic Ligand Field: A Functional Source of FeL₄ Enabled by Labile Dinitrogen Binding

Probing for Four-Coordinate Zerovalent Iron in a π-Acidic Ligand Field: A Functional Source of FeL₄ Enabled by Labile Dinitrogen Binding