The reactivity of the secondary phosphide KP(Pr)Ter (1) (Ter = 2,6-bis-(2,4,6-trimethylphenyl)phenyl) toward small molecules is reported. Phosphide 1 displays distinct nucleophilic character and reacts selectively with chalcogens (S, Se), heteroallenes (CO, PrNCS), and an acyl chloride (AdCOCl) to give the corresponding dichalcogenophosphinates (2a, 3), phosphanyl formate (5), thiocarbamoylphosphane (6a), or acylphosphane (7a), respectively. Furthermore the follow-up chemistry of these products was investigated. 2a was converted to a PSPS ligand (2b) which forms a Au(I) complex (2c) with (MeS)AuCl. Likewise, a gold complex of 7a was prepared. All species were isolated and fully characterized.
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Reaction of potassium phosphide KP(iPr)Ter with chalcogens, heteroallenes and an acyl chloride.
Dalton Trans
November 2021
Institut für Chemie, Universität Rostock, Albert-Einstein-Straße 3a, D-18059 Rostock, Germany.
The reactivity of the secondary phosphide KP(Pr)Ter (1) (Ter = 2,6-bis-(2,4,6-trimethylphenyl)phenyl) toward small molecules is reported. Phosphide 1 displays distinct nucleophilic character and reacts selectively with chalcogens (S, Se), heteroallenes (CO, PrNCS), and an acyl chloride (AdCOCl) to give the corresponding dichalcogenophosphinates (2a, 3), phosphanyl formate (5), thiocarbamoylphosphane (6a), or acylphosphane (7a), respectively. Furthermore the follow-up chemistry of these products was investigated.
View Article and Find Full Text PDFChalcogen extrusion from heteroallenes and carbon monoxide by a three-coordinate rh(i) disilylamide.
Inorg Chem
April 2015
‡Department of Chemistry and Biochemistry, St. Catherine University, St. Paul, Minnesota 55105, United States.
We report the reactions of several heteroallenes (carbon disulfide, carbonyl sulfide, and phenyl isocyanate) and carbon monoxide with a three-coordinate, bis(phosphine)-supported Rh(I) disilylamide (1). Carbon disulfide reacts with 1 to afford a silyltrithiocarbonate complex similar to an intermediate previously invoked in the deoxygenation of CO2 by 1, and prolonged heating affords a structurally unusual μ-κ(2)(S,S'):κ(2)(S,S')-trithiocarbonate dimer. Carbonyl sulfide reacts with 1 to afford a structurally unique Rh(SCNCS) metallacycle derived from two insertions of OCS and N-to-O silyl-group migrations.
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