Heterometallic Pt–Ag and Pt2Ag transition metal complexes
| Autor: | Petra Zoufalá, Amaya del Villar, Gerd Rheinwald, Tobias Rüffer, Heinrich Lang, Thomas Stein |
|---|---|
| Rok vydání: | 2007 |
| Předmět: |
chemistry.chemical_classification
Stereochemistry Acetylide Organic Chemistry chemistry.chemical_element Alkyne Crystal structure Biochemistry Solid state structure Inorganic Chemistry Metal Crystallography chemistry.chemical_compound Transition metal chemistry visual_art Materials Chemistry visual_art.visual_art_medium Molecule Physical and Theoretical Chemistry Platinum |
| Zdroj: | Journal of Organometallic Chemistry. 692:5203-5210 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2007.08.002 |
| Popis: | Complexes of type { cis -[Pt](μ-σ,π-C CPh) 2 }AgX ( 3a , [Pt] = (bipy′)Pt, X = FBF 3 ; 3b , [Pt] = (bipy′)Pt, X = FPF 5 ; 3c , [Pt] = (bipy)Pt, X = OClO 3 ; 3d , [Pt] = (bipy′)Pt, X = BPh 4 ; bipy′ = 4,4′-dimethyl-2,2′-bipyridine; bipy = 2,2′-bipyridine) are accessible by combining cis -[Pt](C CPh) 2 ( 1a , [Pt] = (bipy′)Pt; 1b , [Pt] = (bipy)Pt) with equimolar amounts of [AgX] ( 2a , X = BF 4 ; 2b , X = PF 6 ; 2c , X = ClO 4 ; 2d , X = BPh 4 ). In 3a – 3d the platinum(II) and silver(I) ions are connected by σ- and π-bonded phenyl acetylide ligands. When the molar ratio of 1 and 2 is changed to 2:1 then trimetallic [{ cis -[Pt](μ-C CPh) 2 } 2 Ag]X ( 8a , [Pt] = (bipy)Pt, X = BF 4 ; 8b , [Pt] = (bipy′)Pt, X = PF 6 ; 8c , [Pt] = (bipy)Pt, X = BF 4 ) is produced. The solid state structure of 8a was determined by single X-ray crystal structure analysis. In 8a the silver(I) ion is embedded between two parallel oriented cis -[Pt](C CPh) 2 units. Within this structural arrangement the phenyl acetylides of individual [Pt](C CPh) 2 entities possess a μ-bridging position between Pt(II) and Ag(I). In addition, a very weak dative Pt → Ag interaction is found (Pt–Ag 2.8965(3) A). The respective silver carbon distances Ag–C α (2.548(7), 2.447(7) A) and Ag–C β (3.042(7), 2.799(8) A)(PtC α C β Ph) confirm this structural motif. Complexes 8a – 8c isomerize in solution to form trimetallic [{ cis -[Pt](μ-σ,π-C CPh) 2 } 2 Ag]X ( 9a , [Pt] = (bipy)Pt, X = BF 4 ; 9b , [Pt] = (bipy′)Pt, X = PF 6 ; 9c , [Pt] = (bipy)Pt, X = ClO 4 ). In the latter molecules the organometallic cation [{ cis -[Pt](μ-σ,π- C CPh) 2 } 2 Ag] + is set-up by two nearly orthogonal positioned [Pt](C CPh) 2 entities which are hold in close proximity by the group-11 metal ion. Within this assembly all four PhC C units are η 2 -coordinated to silver(I). A possible mechanism for the formation of 9 is presented. |
| Databáze: | OpenAIRE |
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