Synthesis and Structural Characterization of Base-Stabilized Oligomeric Heterovinylidenes
| Autor: | Thomas C. W. Mak, Wang-Kin Chiu, Wing-Por Leung |
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| Rok vydání: | 2013 |
| Předmět: |
Models
Molecular chemistry.chemical_classification Magnetic Resonance Spectroscopy Vinyl Compounds Molecular Structure Chemistry Metalation Stereochemistry Salt (chemistry) chemistry.chemical_element Crystallography X-Ray Medicinal chemistry Cycloaddition Inorganic Chemistry chemistry.chemical_compound Indenes Cyclization Organometallic Compounds Moiety Lithium Physical and Theoretical Chemistry Diiron nonacarbonyl Tin Phosphine |
| Zdroj: | Inorganic Chemistry. 52:9479-9486 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic4011345 |
| Popis: | Metalation of the (iminophosphoranyl)phosphine PPh2CH2(PPh2═NSiMe3) (1) with an equimolar amount of n-BuLi afforded the monolithium salt [Li{CH(PPh2)(PPh2═NSiMe3)}(THF)2] (2). The reaction of 2 with GeCl2·1,4-dioxane has led to the formation of a germavinylene moiety, which trimerized to form a new heterocyclic cage compound, [{(PPh2═NSiMe3)(PPh2)C═Ge:}{(PPh2═NSiMe3)(PPh2)C}2Ge→Ge:] (3). A similar reaction of the lithium methanide complex 2 with SnCl2 afforded the stannavinylidene moiety, which underwent a "head-to-tail" cycloaddition to form a stable 1,3-distannacyclobutane, 4. A trapping reaction of 4 with diiron nonacarbonyl gave the novel iron stannavinylidene complex 5. The solid-state structure analysis of 5 reveals that it contains two stannavinylidene moieties bonded in a Sn-P "head-to-tail" fashion, with one of the tin(II) centers coordinating to a Fe(CO)4 moiety. The X-ray structures of 2-5 have been determined by X-ray crystallography. In addition, the dynamic behavior of 5 has been studied by means of variable-temperature (31)P and (119)Sn NMR spectroscopy. |
| Databáze: | OpenAIRE |
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