Bonding and Reactivity in Terminal versus Bridging Arenide Complexes of Thorium Acting as Th <sup>II</sup> Synthons
نویسندگان
چکیده
Thorium redox chemistry is extremely scarce due to the high stability of ThIV. Here we report two unique examples thorium arenide complexes prepared by reduction a ThIV-siloxide complex in presence naphthalene, mononuclear [K(OSi(OtBu)3)3Th(η6-C10H8)] (1) and inverse-sandwich [K(OSi(OtBu)3)3Th]2(μ-η6,η6-C10H8)] (2). The electrons stored these allow broad range substrates (N2O, AdN3, CO2, HBBN). Higher reactivity was found for 1 which reacts with diazoolefin IDipp=CN2 yield unexpected ThIV amidoalkynyl 5 via terminal N-heterocyclic vinylidene intermediate. This work showed that arenides can act as convenient redox-active ligands implementing thorium-ligand cooperative multielectron transfer be tuned binding mode.
منابع مشابه
Reactivity of Cobalt(III) Amine-Thiolate Complexes with Terminal and Bridging Thiolate Functions towards Hydrogen Peroxide
Reprint requests to Dr. B. Kersting. E-mail: [email protected] Z. Naturforsch. 55 b, 1179-1187 (2000); received August 17, 2000 Cobalt Complexes, Amine-Thiolate Ligands, Sulfinate Complexes The reactivity of Co111 amine-thiolate complexes with terminal and bridging thiolate func tions towards oxidizing agents has been investigated. The mononuclear Co N3S3 complex [Coni(L1)] (2)...
متن کاملa fundamental study of "histiriographic metafiction", and "literary genres", as introduced in "new historical philosophy", and tracing them in the works of julian barnes.
abstract a fundamental study of “historio-graphic metafiction” and “literary genres”, as introduced in “new historical philosophy”, and tracing them in the works of julian barnes having studied the two novels, the porcupine and arthur & george, by julian barnes, the researcher has applied linda hutcheon’s historio-graphic metafictional theories to them. the thesis is divided into five cha...
15 صفحه اولThe Th=C double bond: an experimental and computational study of thorium poly-carbene complexes.
The first thorium poly-carbene complexes [(Ph(2)P=S)(2)C](2)Th(DME) (2) and [{[(Ph(2)P=S)(2)C](3)Th}Li(2)(DME)](n) (3) have been prepared and structurally characterized. DFT calculations reveal that the Th=C bond is polarized toward the nucleophilic carbene carbon atom, which is further verified by the experimental observation that the Th=C bond shows a nucleophilic behavior with Ph(2)CO.
متن کاملMixed sandwich thorium complexes incorporating bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl ligands: synthesis, structure and reactivity.
The Th(iv) mixed-sandwich halide complexes Th(COT(TIPS2))Cp*X (where COT(TIPS2) = 1,4-{Si(i)Pr(3)}(2)C(8)H(6), X = Cl, I) have been synthesised, and structurally characterised. When Th(COT(TIPS2))Cp*I is reduced in situ in the presence of CO(2), a mixture of dimeric carboxylate and oxalate complexes {Th(COT(TIPS2))Cp*}(2)(μ-κ(1):κ(2)-CO(3)) and {Th(COT(TIPS2))Cp*}(2)(μ-κ(2):κ(2)-C(2)O(4)) are f...
متن کاملThorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions
Despite the burgeoning field of uranium-ligand multiple bonds, analogous complexes involving other actinides remain scarce. For thorium, under ambient conditions only a few multiple bonds to carbon, nitrogen, oxygen, sulfur, selenium and tellurium are reported, and no multiple bonds to phosphorus are known, reflecting a general paucity of synthetic methodologies and also problems associated wit...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Angewandte Chemie
سال: 2023
ISSN: ['1521-3773', '1433-7851', '0570-0833']
DOI: https://doi.org/10.1002/ange.202215846