We report the synthesis and properties of the much sought-after tris(1,1,3,3-tetramethylguanidinyl) phosphine P(tmg) , a crystalline, superbasic phosphine accessible through a short and scalable procedure from the cheap and commercially available bulk chemicals 1,1,3,3-tetramethylguanidine, tris(dimethylamino)-phosphine and phosphorus trichloride. The new phosphine exhibits exceptional electron donor properties and readily forms transition metal complexes with gold(I), palladium(II) and rhodium(I) precursors. The formation of zwitterionic Lewis base adducts with carbon dioxide and sulfur dioxide was explored. In addition, the complete series of phosphine chalcogenides was prepared from the reaction of P(tmg) with N O and the elemental chalcogens.
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http://dx.doi.org/10.1002/chem.202104021 | DOI Listing |
Inorg Chem
January 2025
School of Chemistry, University of Hyderabad, Hyderabad500046, India.
A Ce(III) phosphinate and a Ce(IV) phosphostibonate have been assembled by the reaction of a phosphinic acid and phosphostibonate with Ce(III) salts. Single crystal X-ray diffraction (SCXRD) studies reveal the formation of a rare triangular Ce(III) oxo-cluster [Ce(PhCHPO)]Cl(CHOH)(HO)] () and a fascinating hexanuclear oxo-cluster containing Ce(IV) ions [Ce (-ClCHSb)(μ-O)(μ-O)(-BuPO)(μ-OCH)] (). The molecular architecture of showcased an interesting correlation with platonic solids, wherein the Ce(IV), Sb(V), and P(V) ions were found to be present in vertices of an octahedron, a tetrahedron, and a cube, respectively.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry and Chemistry Institution for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ConspectusControlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C-C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies.
View Article and Find Full Text PDFACS Nano
January 2025
Department of Chemistry and Applied Biosciences, Institute for Chemical and Bioengineering, ETH Zurich, 8093 Zurich, Switzerland.
Single-atom heterogeneous catalysts (SACs) are potential, recoverable alternatives to soluble organometallic complexes for cross-coupling reactions in fine-chemical synthesis. When developing SACs for these applications, it is often expected that the need for ligands, which are essential for organometallic catalysts, can be bypassed. Contrary to that, ligands remain almost always required for palladium atoms stabilized on commonly used functionalized carbon and carbon nitride supports, as the catalysts otherwise show limited activity.
View Article and Find Full Text PDFChembiochem
January 2025
Universidade Federal de São Carlos: Universidade Federal de Sao Carlos, Departament of Chemistry, 13565-905, São Carlos, BRAZIL.
In this work, we studied six Ruthenium(II)-diphosphine compounds containing different mercapto ligands (N-S), with general formula [Ru(N-S)(dppm)2]Cl (dppm = 1,1-bis(diphenylphosphino)methane). These compounds were characterized by several techniques (NMR [1H, 31P(1H), and 13C], HRMS, IR, UV-Vis and XRD) and their purity confirmed by elemental analysis. DLS experiments revealed low diameters and polydispersity indexes, and positive log P values in n-octanol/PBS indicated their preference for the organic phase.
View Article and Find Full Text PDFOrg Biomol Chem
January 2025
College of Chemical Engineering, Sichuan University of Science & Engineering, Zigong 643000, China.
In this study, phosphoramide compounds were successfully synthesized a series of reaction transformations from P(O)H compounds. The process began with the formation of P-Se-Ar bonds, facilitated by the synergistic effect of phenylboronic acid, selenium, and appropriate ligands in the presence of copper. Following this, nucleophilic substitution reactions with amine compounds were conducted to create P-N bonds.
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