The binding of an alkene by Ni(tfd)(2) [tfd = S(2)C(2)(CF(3))(2)] is one of the most intriguing ligand-based reactions. In the presence of the anionic, reduced metal complex, the primary product is an interligand adduct, while in the absence of the anion, dihydrodithiins and metal complex decomposition products are preferred. New kinetic (global analysis) and computational (DFT) data explain the crucial role of the anion in suppressing decomposition and catalyzing the formation of the interligand product through a dimetallic complex that appears to catalyze alkene addition across the Ni-S bond, leading to a lower barrier for the interligand adduct.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/ja2107965 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Unraveling the Mechanism and Influence of Auxiliary Ligands on the Isomerization of Neutral [P,O]-Chelated Nickel Complexes for Olefin Polymerization.
J Org Chem
January 2025
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China.
The copolymerization of ethylene with polar monomers presents a significant challenge. While palladium catalysts have shown promise, nickel catalysts are more economical but suffer from poor activity. Previous studies suggest that the isomerization step involved in the nickel-catalyzed polymerization may influence the catalyst activities.
View Article and Find Full Text PDFThe divergent reactivity of β-diketiminato aluminium hydrides with organophosphoryl compounds.
Dalton Trans
January 2025
Institute of Inorganic Chemistry, Georg-August-Universität Göttingen, Göttingen Tammannstrasse 4, D-37077, Germany.
The reactions of LAlH (L = HC(CMeNAr), Ar = 2,6-PrCH) (1) with diphenylphosphane oxide [PhP(O)H], diphenylphosphinamide [PhP(O)NH], and diaryl/alkyl phosphane [(RO)P(O)H (R = Ph, or Pr)] afford their corresponding compounds with compositions LAl(H)OP(Ph) (2), LAl[OP(Ph)] (3), LAl{[N(H)P(O)(Ph)][OP(Ph)]} (4), LAl(OPr) (5), and LAl(OPh) (6), respectively. These reactions probably undergo a process of dehydrogenation coupling, deaminating dehydrogenation coupling, or chain-breaking coupling. It is noteworthy to mention that the reaction of compound 1 with 2 equiv.
View Article and Find Full Text PDFInfrared Ion Spectroscopy of Gaseous [Cu(2,2'-Bipyridine)]: Investigation of Jahn-Teller Elongation Versus Compression.
J Phys Chem A
January 2025
Institute for Molecules and Materials, FELIX Laboratory, Radboud University, Toernooiveld 7, 6525 ED Nijmegen, The Netherlands.
Symmetry breaking is ubiquitous in chemical transformations and affects various physicochemical properties of materials and molecules; Jahn-Teller (JT) distortion of hexa-coordinated transition-metal-ligand complexes falls within this paradigm. An uneven occupancy of degenerate 3d-orbitals forces the complex to adopt an axially elongated or compressed geometry, lowering the symmetry of the system and lifting the degeneracy. Coordination complexes of Cu are known to exhibit axial elongation, while compression is far less common, although this may be due to the lack of rigorous experimental verification.
View Article and Find Full Text PDFP-P Coupling and Terminal Metal-Phosphorus Intermediates.
J Am Chem Soc
January 2025
Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Terminal metal-phosphorus (M-P) complexes are of significant contemporary interest as potential platforms for P-atom transfer (PAT) chemistry. Decarbonylation of metal-phosphaethynolate (M-PCO) complexes has emerged as a general synthetic approach to terminal M-P complexes. M-P complexes that are stabilized by strong M-P multiple bonds are kinetically persistent and isolable.
View Article and Find Full Text PDFPhotoregulation of the biosynthetic activity of fungus using colloidal solutions of biogenic metal nanoparticles and low-intensity laser radiation.
Bioengineered
December 2025
Department of Translational Medical Bioengineering, National Technical University of Ukraine "Igor Sikorsky Kyiv Polytechnic Institute", Kyiv, Ukraine.
This article presents new data on the integrated use of colloidal solutions of nanoparticles and low-intensity laser radiation on the biosynthetic activity of the medicinal mushroom . Traditional mycological methods, colloidal solutions of biogenic metals, and unique photobiological methods have also been used. It was found that colloidal solutions of nanoparticles of all metals used increased the growth characteristics of (55-60%), while irradiation of the fungal inoculum with laser light in a medium with nanoparticles reduced the growth activity of mycelia by 12.
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!