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The reactions of the tetrahedral diphosphorus [CpMo(CO)(η-P)] (; Cp = CH) complex with Ag[Al{OC(CF)}] (AgTEF) () and Ag[FAl{OC(CF)(CF)}] (AgFAl) () were studied. The first reaction led to the formation of the [Ag(η-)(η:η-)][TEF] () dimer and the [Ag(η:η-)] [TEF] () coordination polymer, whereas the second reaction afforded the [Ag(η:η-)(η-CHCl)(η-CH)][FAl] () or the [Ag(η-)(η:η-)][FAl] () dimer and the [Ag(η:η-)] [FAl] () coordination polymer. In each case, the products obtained depended on the ratio of the reactants and/or the synthetic procedure.
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http://dx.doi.org/10.1002/ejic.201700646 | DOI Listing |
Dalton Trans
April 2025
Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès, 1-11, E-08028, Barcelona, Spain.
The synthesis, complexation and main catalytic applications in enantioselective homogeneous catalysis of enantiopure single-atom-bridged diphosphorus ligands ((RR)P-X-P(RR); X = CR, NR, O) is reviewed, covering the literature up to the beginning of 2025. The information is organised by ligand type, with unsubstituted methylene-bridged (-CH-) and substituted amino-bridged (-NR-) diphosphorus ligands being by far the most common type of ligands. The perspective review is completed by the analysis of all reported crystal structures of bidentate monometallic complexes with the ligands.
View Article and Find Full Text PDFJ Am Chem Soc
February 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 PDFOrg Lett
January 2025
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.
A series of chiral hybrid diphosphorus ligands incorporating a conformationally flexible tropos diphenylmethane-based phosphoramidite unit have been developed and evaluated in the Rh-catalyzed asymmetric hydrogenation of 2-(1-arylvinyl)anilides and α-enamides, leading to up to >99% yield and 99% enantiomeric excess. Preliminary results from comparative studies showcased the extraordinary catalytic performance of these chiral tropos phosphine-phosphoramidite ligands, with a competency essentially superior to those of well-established ligands with a regular rigid backbone.
View Article and Find Full Text PDFOrganometallics
June 2024
Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77842-3012, United States.
Photolyses of -Fe(CO)(As((CH) )As) ( = , 10; , 12; , 14) in the presence of PMe, or reactions of -[Fe(CO)(NO)(As((CH) )As)] BF and -BuN Cl, afford the air stable title complexes As((CH) )As (-) in 79-34% yields. With , the , and , isomers are separable and each is crystallographically characterized. With ,, the isomers rapidly interconvert by homeomorphic isomerization, but each crystallizes (contrathermodynamically) as an , isomer.
View Article and Find Full Text PDFInorg Chem
October 2024
Department of Chemistry, University of California, Davis, Davis, California 95616, United States.
Phosphorus is critical to humans on many fronts, yet we do not have a mechanistic understanding of some of its most basic transformations and reactions─namely the oligomerization of white phosphorus to red. With heat or under ultraviolet (UV) exposure, it has been experimentally demonstrated that white phosphorus dissociates into diphosphorus units which readily form red phosphorus. However, the mechanism of this process is unknown.
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