XPS Investigations of (1,4,7-trimethyl-1,4,7-triazacyclononane)RhMe3 and [1,1,1-tris((dimethylphosphino)methyl)ethane]RhMe3 and Their Rh−C Cleavage Derivatives. Comparison of Hard- and Soft-Ligated Rhodium Organometallics
| Autor: | a Chunming Wang, a Roy S. Lu, John R. Sowa, Jr., b,c, a Thomas C. Flood, a Lin Wang, Paul G. Gassman, b, and |
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| Rok vydání: | 1996 |
| Předmět: |
Organic Chemistry
Inorganic chemistry Binding energy chemistry.chemical_element Ether Crystal structure Medicinal chemistry Rhodium Inorganic Chemistry Metal chemistry.chemical_compound chemistry X-ray photoelectron spectroscopy Bromide visual_art visual_art.visual_art_medium Molecule Physical and Theoretical Chemistry |
| Zdroj: | Organometallics. 15:4240-4246 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om9601099 |
| Popis: | The new molecules P3RhMe3-n(OTf)n are reported (n = 0−2; P3 = MeC(CH2PMe2)3; OTf = OS(O)2CF3). The known fac-(Me3P)3RhMe3 was converted to mer-(Me3P)3RhMe3-nCln (n = 1, 2) by cleavage with HCl in ether. X-ray photoelectron spectra (XPS) of these were recorded, and all except the P3RhMe3-nCln series afforded clean spectra. XPS were also obtained for the known CnRhMe3-nXn (n = 0−2; X = Cl, Br, OTf; Cn = 1,4,7-trimethyl-1,4,7-triazacyclononane), CnRhX3 (X = Cl, Br), CnRhMe(OH)(OTf), and [CnRhMe2(CO)]OTf. An X-ray crystal structure of P3RhMe3 is reported, and the geometry at the metal is compared among P3RhMe3, (Me3P)3RhMe3, and CnRhMe3. Core binding energies (BEs) for the series L3RhMe3-nXn (L3 = Cn, P3) change linearly with n for a given L3 and X. For CnRhMe3-nXn, replacement of methyl by chloride or bromide gives similar ΔBE values (∼0.7 eV), while triflate-for-methyl substitution gives a much larger ΔBE (1.2 eV). Triflate-for-methyl substitution in P3RhMe3-n(OTf)n, however, causes a ΔBE of only 0.8 eV. Th... |
| Databáze: | OpenAIRE |
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