Chemistry of polynuclear allenyl complexes: The μ-η1 : η2-allenyl diruthenium system Ru2(CO)6(μ-PPh2)(μ-η1 :η2-C(Ph)CCH2). Dimetallocycles via CC, CN and CS bond forming reactions and the X-ray structure of Ru2(CO)6(μ-PPh2)[μ-η1 : η1-PhCC{C(EtS)N(H)tBu}CH2]
| Autor: | Enrico Sappa, Antonio Tiripicchio, Arthur J. Carty, Susan M. Breckenridge, Maria Angela Pellinghelli |
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| Rok vydání: | 1994 |
| Předmět: |
chemistry.chemical_classification
Double bond Chemistry Stereochemistry Allene Isocyanide Organic Chemistry chemistry.chemical_element Bridging ligand Nuclear magnetic resonance spectroscopy Crystal structure Metallacycle Biochemistry Ruthenium Inorganic Chemistry chemistry.chemical_compound Crystallography Materials Chemistry Physical and Theoretical Chemistry |
| Zdroj: | Journal of Organometallic Chemistry. 471:211-219 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/0022-328x(94)88127-8 |
| Popis: | The μ-η1: η2-allenyl complex Ru2(CO)6(μ-η1 : η2-C(Ph)CCH2)(μ-PPh2) (1), which has a structure with Cα(Ph) coordinated to one ruthenium atom and the CβCγ double bond attached to the second metal atom, undergoes regiospecific attack at Cβ by tBuNC to afford quantitative yields of an adduct Ru2(CO)6[μ-η1: η1-PhCC(CNtBu)CH2](μ-PPh2) (3), which has been characterized by microanalysts, IR and NMR spectroscopy. Complex 3 is converted into Ru2(CO)6(μ-PPh2)[μ-η1:η1-PhC C{C(EtNH)N(H)tBu}CH2](4) and Ru2 (CO)6(μ-PPh2)[μ-η1:η1-PhCC{C(EtS)N(H)tBU}CH2] (5) by the addition of EtNH2 or EtSH respectively across the CN bond of the ‘carbon coordinated’ isonitrile. The X-ray structure of 5 has been determined. Crystal data: C34H 32NO6PRU2S · 0.5CH2Cl2, monoclinic, space group P21/n, a = 11.486(5), b = 14.956(5), c = 21.465(8) A, β = 101.82(2)°, Z = 4, R = 0.032, Rw = 0.041. The nature of the amidinium and thioamidinium centres in 4 and 5 and the formation of the CC, CN and CS bonds in 1 to form 3, 4 and 5 are discussed. |
| Databáze: | OpenAIRE |
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