The first zerovalent germanium complex ("germylone") 3, [Si(Xant)Si]Ge, stabilized by a chelating bis(N-heterocyclic silylene)xanthene donor ligand 1 was successfully synthesized via the dechlorination of the corresponding {[Si(Xant)Si]GeCl}Cl complex 2 with KC; it was structurally and spectroscopically characterized, and also studied by density functional theory (DFT) calculations. Natural bond orbital (NBO) analysis of 3 unambiguously exhibits two lone pairs of electrons (one σ-type lone-pair and one 3p(Ge) lone-pair) on the zerovalent Ge atom. This is why the Ge atom can form the corresponding mono- and bis-AlBr Ge → Al Lewis adducts [Si(Xant)Si]Ge(AlBr) 4 and [Si(Xant)Si]Ge(AlBr) 5, respectively. Due to the electron-rich character of the Ge atom, the germylone 3 displayed quite unusual reactivities. Thus, the reaction of 3 with 9-borabicyclo[3.3.1]nonane (9-BBN) as a potential Lewis acid furnished the first boryl(silyl)germylene complex 6, possessing a heteroallylic B···Ge···Si π-conjugation. When 3 was allowed to react with Ni(cod) (cod = 1,5-cyclooctadiene), the unique {[Si(Xant)Si]Ge}Ni complex with a three-membered ring GeNi-metallacycle was obtained via reductive coupling of two Ge atoms on the Ni center. Moreover, 3 was suitable to form a frustrated Lewis pair (FLP) with BPh, which was capable of heterolytic H cleavage at 1 atm and room temperature, representing, for the first time, that a metallylone could be applied in FLP chemistry.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.8b11605 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
An isolable boron-centered radical anion stabilized by a carbazole moiety.
Dalton Trans
January 2025
Hebei Center for New Inorganic Optoelectronic Nanomaterial Research, Hebei Key Laboratory of Heterocyclic Compounds, College of Chemical Engineering and Materials, Handan University, Handan 056002, P. R. China.
The isolation of a stable persistent carbazole-stabilized boron-centered monoradical anion 1˙, which has a high spin density at the B atom, has been reported. It is characterized using the crystal structure and UV-vis absorption spectrum, as well as electron paramagnetic resonance spectroscopy. Interestingly, the B-N bond was activated by the boron-centered radical anion 1˙, which had not been reported before.
View Article and Find Full Text PDFButyl Imidates: Highly Stable and Isolable Synthetic Intermediates.
J Org Chem
January 2025
U.S. Process Chemistry, CMC Synthetics Platform, Sanofi, 350 Water Street, Cambridge, Massachusetts 02141, United States.
Imidates are versatile synthetic intermediates that contain ambiphilic reactivity, making them valuable pharmaceutically relevant synthons. Despite their extensive utility, imidates are typically generated in situ rather than isolated due to their inherent instability. This report details a systematic study that led to the discovery of an isolable imidate hydrogen chloride (HCl) salt that exhibits high tolerance to hydrolysis, thereby improving process control and facilitating downstream transformations.
View Article and Find Full Text PDFMolecular Phosphide Complexes of Zirconium.
J Am Chem Soc
January 2025
Department of Chemistry, University of Pennsylvania, 231 S 34th St, Philadelphia, Pennsylvania 19104, United States.
Molecular Zr phosphides are extremely rare, with no examples containing a one-coordinated and terminal triple-bonded phosphorus atom. We report here an isolable and relatively stable Zr phosphide complex, [(PN)Zr≡P{μ-Na(OEt)}] (), stemming from a cyclometalated Zr-hydride, [(PN)(PN')Zr(H)] (), and NaPH. Complex is prepared from two- or one-electron reductions of precursors [(PN)ZrCl] () or metastable Zr[(PN)ZrCl], respectively.
View Article and Find Full Text PDFThCTi@(6)-C: Th═C Double Bond in a Mixed Actinide-Transition Metal Cluster.
J Am Chem Soc
January 2025
College of Chemistry, Chemical Engineering and Materials Science, and State Key Laboratory of Radiation Medicine and Protection, Soochow University, Suzhou, Jiangsu 215123, P. R. China.
A thorium-carbon double bond that corresponds to the sum of theoretical covalent double bond radii has long been sought after in the study of actinide-ligand multiple bonding as a synthetic target. However, the stabilization of this chemical bond remains a great challenge to date, in part because of a relatively poor energetic matching between 5f-/6d- orbitals of thorium and the 2s-/2p- frontier orbitals of carbon. Herein, we report the successful synthesis of a thorium-carbon double bond in a carbon-bridged actinide-transition metal cluster, i.
View Article and Find Full Text PDFStructures and Properties of Axially Chiral (2E,4E,6Z,8Z)-Nona-2,4,6,8-Tetraenoate Derivatives Highly Substituted by Aryl Groups.
Chemistry
January 2025
Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
Unprecedented (2E,4E,6Z,8Z)-nona-2,4,6,8-tetraenoate derivatives highly substituted by aryl groups have been synthesized by the reaction of rhodium complexes having aryl-substituted hexa-1,3,5-trienyl ligands with acrylates. These compounds have potential axial chirality, and their enantiomers are isolable by the chiral HPLC technique. Although the racemization barrier of isolated enantiomers was not high, it was found that a cyclic dimer synthesized by head-to-tail transesterification of a modified analog has quite a stable axial chirality even at a high temperature.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!