The synthesis of five-membered P-heterocyclic iron(0) complexes possessing a P-H unit and two heteroatoms (E = O, N), directly bound to phosphorus, is described. Initial problems to achieve access "classical" reduction of P-Cl bonds of P-heterocycle complexes, , leading to P-P coupling, could be solved by a "combined two-step" reduction/complexation. The use of K[Fe(CO)H] not only opened access to such heterocyclic phosphane Fe(CO) complexes but also allowed the synthesis of sterically non-shielded 'secondary' heterocyclic phosphane complexes. Spectroscopic and structural parameters are discussed.
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Angew Chem Int Ed Engl
December 2024
Tsinghua University, Department of Chemistry, 1 Qinghuayuan, Haidian District, 100084, Beijing, CHINA.
The in-depth research on the charge transport properties of BN-embedded polycyclic aromatic hydrocarbons (BN-PAHs) still lags far behind studies of their emitting properties. Herein, we report the successfully synthesis of novel ladder-type BN-PAHs (BCNL1 and BCNL2) featuring a highly ordered BC3N2 acene unit, achieved via a nitrogen-directed tandem C-H borylation. Single-crystal X-ray diffraction analysis unambiguously revealed their unique and compact herringbone packing structures.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
State key laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, 15 Yu Cai Road, Guilin, 541004, China.
Skeletal editing represents an attractive strategy for adding complexity to a given molecular scaffold in chemical synthesis. Isodesmic reactions provide a complementary skeletal editing approach for the redistribution of chemical bonds in chemical synthesis. However, catalytic enantioselective isodesmic reaction is extremely scarce and enantioselective isodesmic reaction to synthesize atropisomeric compounds is unknown.
View Article and Find Full Text PDFChem Sci
November 2024
Institute of Inorganic Chemistry, University of Duisburg-Essen Universitätsstraße 5-7 D-45141 Essen Germany https://www.uni-due.de/ak_schulz/index_en.php.
1,3-Diphosphaallenes are a new class of heavier heteroallenes and show a fascinating chemical behavior and reactivity. Herein we report on the room temperature transformation of gallaphosphene LGa(OCP)PGaL 1 (L = HC[C(Me)N(Ar)], Ar = 2,6-i-PrCH) to the six-membered metallaheterocycle LGa(PCP)OGaL 2 featuring a LGa-substituted 1,3-diphosphaallene unit. The possible mechanism of formation of 2 is supported by quantum chemical calculations, which revealed that the formation of 2 is energetically more favorable ( 2 kcal mol) than the formation of 1 at ambient temperature.
View Article and Find Full Text PDFIUCrdata
November 2024
EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife KY16 9ST, United Kingdom.
The title racemic oxopyrrolidine compound, CHNO, contains three stereogenic centres and crystallizes with two mol-ecules in the asymmetric unit. The five-membered pyrrolidine rings in both mol-ecules exhibit envelope conformations. The -ethyl group of one of the mol-ecules is disordered over two sets of sites in a 0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore, Singapore.
Polycyclic aromatic diradical(oid) molecules are attracting significant attention because of their unique electronic and magnetic properties as well as their applications as functional materials. While diradical(oid) molecules bearing five-membered rings have been extensively investigated, those bearing seven-membered rings are relatively fewer. Herein, we report the synthesis of azapentabenzodihomocorannulene dication and diradical molecules.
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