The specific electronic properties of bent o-carborane diphosphine gold(I) fragments were exploited to obtain the first classical carbonyl complex of gold [(DPCb)AuCO](+) (ν(CO)=2143 cm(-1) ) and the diphenylcarbene complex [(DPCb)Au(CPh2 )](+) , which is stabilized by the gold fragment rather than the carbene substituents. These two complexes were characterized by spectroscopic and crystallographic means. The [(DPCb)Au](+) fragment plays a major role in their stability, as substantiated by DFT calculations. The bending induced by the diphosphine ligand substantially enhances π-backdonation and thereby allows the isolation of carbonyl and carbene complexes featuring significant π-bond character.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.201407684 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Program-Modulated Kinetics of Perovskite-Film Growth by Molecular "Thruster" for High-Efficiency and Stable Perovskite Solar Cells.
Angew Chem Int Ed Engl
December 2024
Soochow University, College of Chemistry, Chemical Engineering and Materials Science, Ren-ai Road 199#, Industry Park, 215123, Suzhou, CHINA.
The rapid reaction between lead iodide (PbI2) and formamidinium iodide (FAI) complicates the fabrication of high-quality formamidinium lead iodide (FAPbI3) films. Conventional methods, such as using nonvolatile small molecular additives to slow the reaction, often result in buried interfacial voids and molecule diffusion, compromising the devices' operational stability. In this study, we introduced a molecular "thruster"-a hypervalent iodine (III) compound with three carbonyl groups and a C--I⁺ bond-that possesses coordination and dissociation abilities, enabling programed modulation of perovskite-film growth kinetics.
View Article and Find Full Text PDFLight-Induced Transformations of Donor-Donor Diazo Compounds Derived from N-Sulfonylhydrazones.
Chem Asian J
November 2024
Department of Chemistry, Laboratory of Organic Synthesis & Catalysis, Indian Institute of Technology Roorkee, Roorkee, Uttarakhand, 247667, India.
The donor-donor carbene chemistry field is underdeveloped and often relies on harsh reaction conditions, utilizing either thermal or oxidative process with or without transition-metal catalysts. In this review, we discussed the synthesis and transformation of donor-donor diazo compounds from N-sulfonylhydrazones in the presence of light and base. The N-sulfonylhydrazones are easily accessible from the corresponding carbonyl compounds and sulfonyl hydrazides through condensation.
View Article and Find Full Text PDFBorenium Ion Equivalents Stabilized by BICAAC and Their Implementation as Catalysts in Hydrosilylation of Carbonyls.
Chemistry
November 2024
Department of Chemical Sciences, Indian Institute of Science Education and Research Mohali, Knowledge City, Sector 81, SAS Nagar, Mohali, Punjab, 140306, India.
Hydride abstraction from the borane adduct, (BICAAC) ⋅ BH afforded the hydride bridged dinuclear borenium ion equivalent complexes 1 and 2 that have been characterized by various spectroscopic and spectrometric techniques followed by the assessment of Lewis acidity using the Gutmann-Beckett method. The single crystal X-ray structure of complex 2 revealed the presence of discrete ions in the solid state. The complex (BICAAC) ⋅ BH(OTf) (3), obtained from the reaction of (BICAAC) ⋅ BH with MeOTf, formed the corresponding boronium cations [(BICAAC) ⋅ BH(L)](OTf) on reaction with Lewis bases (L= pyridine (4) and DMAP (5)).
View Article and Find Full Text PDFTheoretical exploration of siloxy carbenes: photogeneration and [2+1] photocyclization mechanisms.
Phys Chem Chem Phys
November 2024
Key Laboratory of Theoretical and Computational Photochemistry of Ministry of Education, Department of Chemistry, Beijing Normal University, Beijing 100875, P. R. China.
Carbenes are highly reactive intermediates central to various organic transformations, particularly within photochemistry. This study investigates siloxy carbenes generated from acyl silanes a 1,2-silyl shift, focusing on their generation and reactivity in excited states, using the multiconfiguration perturbation theory (CASPT2//CASSCF/PCM). Our findings reveal that the presence of an aryl group conjugated with the carbonyl moiety substantially lowers the excitation energy of the singlet nπ* state, enabling the 1,2-Brook rearrangement to proceed directly on the singlet hypersurface.
View Article and Find Full Text PDFComparison of the Efficiency of B-O and B-C Bond Formation Pathways in Borane-Catalyzed Carbene Transfer Reactions Using α-Diazocarbonyl Precursors: A Combined Density Functional Theory and Machine Learning Study.
ACS Catal
October 2024
Department of Chemistry and Material Science, School of chemical Engineering, Aalto University, 02150 Espoo, Finland.
Article Synopsis
- Lewis acidic boranes, like tris(pentafluorophenyl)borane, are identified as effective metal-free catalysts for carbene transfer reactions involving α-diazocarbonyl compounds, which are vital for various functionalization reactions.
- The study challenges the traditional understanding that boranes facilitate carbene generation primarily through a B-O (C=O) intermediate, instead highlighting B-C(=N=N) bond formation as the preferred method for certain substrates.
- By investigating 22 substituents on the α-diazocarbonyl backbone and employing machine learning techniques, the research reveals how electronic properties of these substituents significantly influence the effectiveness of boranes in catalyzing carbene formation
Want 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!