Reversible Complexation of Alkynes by a Germylene

Lai, Ting Yi; Gullett, Kelly L.; Chen, Chia Yuan; Fettinger, James C.; Power, Philip P.

doi:10.1021/acs.organomet.9b00077

Cited by 30 publications

(17 citation statements)

References 27 publications

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“…All hydrogen atoms omitted for clarity (bond length in Å, angles in deg). Ge(1)-P(1) 2.380(3), Ge(1)-Si(1) 2.489(3), Ge(1)-Ge(2) 2.5210 (18), Ge(2)-Cl(2) 2.208(4), Ge(2)-Cl(1) 2.253(3), Ge(2)-Si(6) 2.428(3), Si(1)-Si(2) 2.361(4), Si(2)-C(1) 1.864 (14), P(1)-C(11) 1.807 (13), P(1)-Ge(1)-Si(1) 99.69 (11), P(1)-Ge(1)-Ge(2) 93.80 (9), Si(1)-Ge(1)-Ge(2) 105.64 (9), Cl(2)-Ge(2)-Cl(1) 99.49 (17), Cl(2-Ge(2)-Si(6) 102.67 (14), Cl(1)-Ge(2)-Si(6) 101.21 (12), Cl(2)-Ge(2)-Ge(1) 108.28 (12), Cl(1)-Ge(2)-Ge(1) 116.19 (10), Si(6)-Ge(2)-Ge(1) 125.38(10).…”

Section: Resultsmentioning

confidence: 99%

“…A most unusual reaction of this compound, we observed the regioselective 1,2-migratory insertion of phenylacetylene into one or two of the Ge-Si bonds of 1 (Scheme 1) [5]. While, typically, reactions of silylenes and germylenes with alkynes lead to oxidation and the formation of tetravalent sila-and germacyclopropenes [6][7][8][9][10][11][12], the observed phenylacetylene insertion case benefits from the fact that formation of the vinylgermylene PMe 3 adduct (2) is thermodynamically favored compared to the respective germacyclopropene, which exists as an intermediate on the reaction pathway [13].…”

Section: Introductionmentioning

confidence: 92%

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1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

2020

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The reactions of the PMe3 adduct of the silylated germylene [(Me3Si)3Si]2Ge: with GeCl2·dioxane were found to yield 1,1-migratory insertion products of GeCl2 into one or two Ge–Si bonds. In a related reaction, a germylene was inserted with tris(trimethylsilyl)silyl and vinyl substituents into a Ge–Cl bond of GeCl2. This was followed by intramolecular trimethylsilyl chloride elimination to another cyclic germylene PMe3 adduct. The reaction of the GeCl2 mono-insertion product (Me3Si)3SiGe:GeCl2Si(SiMe3)3 with Me3SiC≡CH gave a mixture of alkyne mono- and diinsertion products. While the reaction of a divinylgermylene with GeCl2·dioxane only results in the exchange of the dioxane of GeCl2 against the divinylgermylene as base, the reaction of [(Me3Si)3Si]2Ge: with one GeCl2·dioxane and three phenylacetylenes gives a trivinylated germane with a chlorogermylene attached to one of the vinyl units.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 92%

1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

2020

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“…In contrast to the metallacyclopropenes of early transition metals, main group elements, and actinides, rare-earth metallacyclopropenes have been neglected for many years . Until 2019, our group prepared the first series of rare-earth metallacyclopropenes from the chloride precursors of rare-earth metals, potassium graphite (KC 8 ), and alkynes .…”

Section: Introductionmentioning

confidence: 99%

Reactivity of Lutetacyclopropene toward Benzyl, Benzoyl, and Trimethylsilyl Nitriles Affording Diversified Lutetium Complexes

Zhu

Liu

et al. 2021

Organometallics

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Although the reaction of metallacyclopropenes toward alkyl and aryl nitriles has been extensively studied, their reactivity toward other types of nitriles, e.g., benzyl and benzoyl nitriles, that often behave multifunctionally was rarely explored. Herein, we demonstrated the unique reactivity of lutetacyclopropene 1 with benzyl, benzoyl, and trimethylsilyl nitriles. Treatment of 1 with 2 equiv of ArCH2CN (Ar = Ph or 2,6-Me2C6H3) led to acyclic lutetium complexes 2 with both keteniminate and vinyl-enamide ligands. Isolation of lutetacyclic enamine intermediate 4 indicates that the formation of 2 proceeds through three key steps: the initial insertion of CN bond into Lu–Csp2 bond giving azalutetacyclopentadiene intermediates 3, tautomerization of 3 via 1,3-H shift providing 4, and subsequent intermolecular proton transfer between 4 and ArCH2CN. However, when 1 was allowed to react with benzoyl or trimethylsilyl nitrile, bis-isocyanide complex 5 was obtained with the release of 1,2-dibenzoyl-1,2-diphenylethene or 1,2-di(trimethylsilyl)-1,2-diphenylethene, respectively. The formation of 2 and 5 represents two previously unreported reaction modes between metallacyclopropenes and nitriles.

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“…This is relevant because of the toxicity of the latter, while the low toxicity of organic germanium derivatives is their key feature, which is important in the development of new materials and agents in general [2–3] . The field of catalysis by germylenes has been intensively developing in recent years, and a number of significant achievements have been attained by now [4–9] …”

Section: Introductionmentioning

confidence: 99%

The Redox Properties of Germylenes Stabilized by N‐Donor Ligands

et al. 2021

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Germylenes, organic compounds of divalent germanium, are often considered as promising catalytic systems efficient in reactions of oxidative addition and reductive elimination, including SET reactions. However, the systematic studies of their redox properties, allowing for the quantitative evaluation of the levels of frontier molecular orbitals and the stability of single electron transfer products, are extremely limited in number. In this work, a series of germylenes with various types of stabilization: N−Ge−N, (N→)C−Ge−C(←N), N−Ge−N(←N), O−Ge−O(←N) и (N→)O−Ge−O(←N) (“−“ ‐a covalent bond, stabilization is achieved by p‐donation of a lone pair of electrons of N or O, “→” ‐donor‐acceptor bond) were characterized by cyclic voltammetry. The results were compared with UV/Vis spectroscopy data and DFT calculations. All germylenes studied in MeCN and THF with Bu4NPF6 as a supporting electrolyte are chemically irreversibly oxidized in the potential range of 0.5–1.4 V vs. Ag/AgCl. In all cases, as estimated by the quantum chemical calculations, the HOMO remains at the covalently unsaturated germanium center although being significantly redistributed over the molecular system. In turn, electroreduction of germylenes is possible only in the presence of a strong electron‐withdrawing substituent or a pyridine ring depleted in electron density donated to germanium. In both cases, the LUMO is localized exactly on these moieties and is absent on the germanium. Thus, the use of stabilizing groups makes it possible both to improve germylene stability and to fine‐tune their HOMO level that determines their ability to participate in oxidative addition reactions.

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Reversible Complexation of Alkynes by a Germylene

Cited by 30 publications

References 27 publications

1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

Reactivity of Lutetacyclopropene toward Benzyl, Benzoyl, and Trimethylsilyl Nitriles Affording Diversified Lutetium Complexes

The Redox Properties of Germylenes Stabilized by N‐Donor Ligands

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