Novel yttrium chelating diamide complexes [(Y[ArN(CH(2))(x)NAr](Z)(THF)(n))(y)] (Z = I, CH(SiMe(3))(2), CH(2)Ph, H, N(SiMe(3))(2), OC(6)H(3)-2,6-(t)Bu(2)-4-Me; x = 2, 3; n = 1 or 2; y = 1 or 2) were made via salt metathesis of the potassium diamides (x = 3 (3), x = 2 (4)) and yttrium triiodide in THF (5,10), followed by salt metathesis with the appropriate potassium salt (6-9, 11-13, 15) and further reaction with molecular hydrogen (14). 6 and 11(Z = CH(SiMe(3))(2), x = 2, 3) underwent unprecedented exchange of yttrium for silicon on reaction with phenylsilane to yield (Si[ArN(CH(2))(x)NAr]PhH) (x = 2 (16), 3) and (Si[CH(SiMe(3))(2)]PhH(2)).
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http://dx.doi.org/10.1039/b400149d | DOI Listing |
Angew Chem Int Ed Engl
November 2024
Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry (AOC), Engesserstr. 15, Geb. 30.45, Karlsruhe, Germany.
The molecular strontium hydride 2 [(Cbz)SrH(L)] (L=benzene, toluene) was isolated and stabilized by employing a sterically demanding carbazole ligand (Cbz=1,8-bis(3,5-ditertbutylphenyl)-3,6-ditertbutylcarbazolyl). Compound 2 was synthesized via phenylsilane metathesis with the corresponding amide (Cbz)SrN(SiMe) and characterized by H NMR, XRD and vibrational spectroscopy methods. We further investigated the stoichiometric reactivity of 2 towards carbon monoxide, azobenzene and trimethylsilylacetylene, showing three distinct reactivity pathways: addition, reduction and deprotonation.
View Article and Find Full Text PDFJ Am Chem Soc
August 2024
Fakultät für Chemie, Technische Universität München, Lichtenbergstraße 4, 85748 Garching bei München, Germany.
A family of chelating aryl-functionalized germylene ligands has been developed and employed in the synthesis of their corresponding 16-electron Ni complexes (DippGeAr·Ni·IPr; Dipp = {[PhPCHSi(Pr)](Dipp)N}; IPr = [{(H)CN(Dipp)}C:]; Dipp = 2,6-PrCH). These complexes demonstrate the ability to cooperatively and reversibly activate dihydrogen at the germylene-nickel interface under mild conditions (1.5 atm H, 298 K).
View Article and Find Full Text PDFJ Org Chem
August 2024
Leibniz Institute for Catalysis at the University of Rostock (LIKAT Rostock), Albert Einstein Str. 29a, Rostock D-18059, Germany.
The organocatalytic formation of an underrepresented family of trisubstituted and tetrasubstituted furans from activated alkenes and acyl chlorides is reported. In a reaction sequence based on P(III)/P(V) redox cycling catalysis, the cyclic phosphine catalysts react with diacylethenes or acyl acrylates in Michael addition, followed by acylation and either an intramolecular Wittig reaction or a ring closure reaction, liberating the furans. The formed phosphine oxides are reduced in situ by phenylsilane as a terminal reductant.
View Article and Find Full Text PDFChemistry
July 2024
Chair of Inorganic and Structural Chemistry, Bielefeld University, Universitätsstraße 25, 33615, Bielefeld.
Chalice-shaped tridentate poly-Lewis acids (PLA) based on the tribenzotriquinacene (TBTQ) scaffold have been synthesised. Stannylation of the alkyne units, attached via phenyl-spacers to the benzhydrylic positions to the TBTQ scaffold, with MeNSnMe afforded the trimethyltin substituted TBTQ derivative. Replacement of these tin functions with other elements resulted in rigid boron- and aluminium-functionalised PLAs.
View Article and Find Full Text PDFJ Am Chem Soc
June 2024
Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University, Tsushima, Okayama 700-8530, Japan.
The catalytic reactions of indoles with CO and phenylsilane afforded indolo[3,2-]carbazoles, where the fused benzene ring was constructed by forming two C-H bonds and four C-C bonds with two CO molecules via deoxygenative conversions. Nine-membered cyclophanes made up of three indoles and three CO molecules were also obtained, where the cyclophane framework was constructed by forming six C-H bonds and six C-C bonds. These multicomponent cascade reactions giving completely different carbocycles were switched simply by choosing the solvent, acetonitrile or ethyl acetate.
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