The First Peralkylated Phosphino(stibino)methanes and Their Organometallic Rhodium Complexes
Autor: | Helmut Werner, Dietmar Stalke, Matthias Manger, Matthias Laubender, Markus Teichert, Justin Wolf |
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Rok vydání: | 1997 |
Předmět: |
chemistry.chemical_classification
Tetraphenylborate Organic Chemistry Cationic polymerization Center (category theory) chemistry.chemical_element General Chemistry Medicinal chemistry Catalysis Rhodium Metal chemistry.chemical_compound chemistry Antimony visual_art visual_art.visual_art_medium Organic chemistry Lone pair Alkyl |
Zdroj: | Chemistry - A European Journal. 3:1442-1450 |
ISSN: | 1521-3765 0947-6539 |
DOI: | 10.1002/chem.19970030910 |
Popis: | The first representatives of phosphino(stibino)methanes R2PCH2Sb-R′2 (3–5) with bulky alkyl or cycloalkyl groups R and R′ were prepared in two steps from Ph3SnCH2I via the isolated stannylated phosphanes Ph3SnCH2PR2 (1, 2) as intermediates. X-ray structural analysis of 5 (R = C6H11, R′ = tBu) reveals that the lone pairs and the substituents R and R′ at phosphorus and antimony and the hydrogen atoms of the CH2 bridge adopt staggered conformations. Treatment of [{C8H12RhCl}2] with 3–5 affords the neutral compounds [Rh-Cl(η4-C8H12)(κ-P-R2PCH2SbR′2)] (6–8), of which 7 and 8 react with CH3MgI to give the corresponding methylrhodium derivatives [RhCH3(η4-C8H12)(κ-P-R2-PCH2SbR′2)] (9, 10). Cationic complexes [Rh(η4-C8H12)(η2-P,Sb-R2PCH2SbR′2)]-X (X = PF6: 11a, 12a, 13; X = BPh4: 11b, 12b) containing the phosphino(stibino)methanes as chelating ligands were obtained either from [{C8H12RhCl}2], R2PCH2SbR′2 and MX, or (for 13) from 8 and AgPF6. Compound 12a (R = iPr, R′ = tBu) was characterized by X-ray crystallography. The PF6 salts 11a, 12a, and 13 react with CH2N2 by insertion of CH2 into the Rh–Sb bond to yield the complexes 14–16, the first examples of transition-metal compounds with Sb ylides as ligands. Treatment of BPh4 salts 11b and 12b with H2 gives the half-sand-wich-type complexes [(η6-C6H5BPh3)Rh(κ2-P,Sb-R2PCH2SbR′2)] (17, 18), in which the tetraphenylborate is coordinated like a substituted arene to the metal center. |
Databáze: | OpenAIRE |
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