Synthese, Struktur und Reaktivität von η1und η3-Allyl-Rhenium-Carbonylen

✍ Scribed by Bernd Aechter; Kurt Polborn; Wolfgang Beck

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: German
• Weight: 285 KB
• Volume: 627
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/1521-3749(200101)627:1<43::aid-zaac43>3.0.co;2-g

✦ Synopsis

Professor Dieter Sellmann zum 60. Geburtstag gewidmet Inhaltsu È bersicht. In (g 3 -C 3 H 5 )Re(CO) 4 la È ût sich ein CO-Ligand durch PPh 3 , Pyridin, Isocyanid sowie Benzonitril substituieren. Mit 1,2-Bis(diphenylphosphino)ethylen, 1,1'-Bis-(diphenylphosphino)ferrocen sowie 1,2-Bis(4-pyridyl)ethan entstehen zweikernige, ligand-verbru È ckte Komplexe. Durch Umsetzung von (g 3 -C 3 H 5 )Re(CO) 4 mit den zweiza È hnigen Chelat-Liganden 1,2-Bis(diphenylphosphino)ethan und 1,3-Bis(diphenylphosphino)propan, (Ph 2 PCH 2 ) 3 CMe sowie 2,2'-Bipyridin (L±L) la È ût sich die g 3 ® g 1 Umlagerung des Allyl-Liganden erzwingen und es bilden sich die g 1 -Allyl-Komplexe (g 1 -C 3 H 5 )Re(CO) 3 (L±L). Bei der Reaktion mit Bis(diphenylphosphino)methan wird der Allyl-Ligand in (g 3 -C 3 H 5 )Re(CO) 4 protoniert und als Propen unter Bildung des Diphosphinomethanid-Komplexes (OC) 3 Re- 8), (g 1 -C 3 H 5 )Re(CO) 3 -(bpy) ( 14), von 19 und 20 sowie von (OC) 3 Re-[Ph 2 P(CH 2 ) 3 PPh 2 ]Cl ( 16) wurden durch Ro È ntgenbeugung bestimmt.

Synthesis, Structure, and Reactivity of g 1 -and g 3 -Allyl Rhenium Carbonyls Abstract. In (g 3 -C 3 H 5 )Re(CO) 4 one CO ligand can be substituted by PPh 3 , pyridine, isocyanide and benzonitrile. With 1,2-bis(diphenylphosphino)ethylene, 1,1'-bis(diphenylphosphino)ferrocene and 1,2-bis(4-pyridyl)ethane dinuclear ligand bridged complexes are obtained. The g 3 -g 1 conversion of the allyl ligand occurs on reaction of (g 3 -C 3 H 5 )Re(CO) 4 with the bidendate ligands 1,2-bis(diphenylphosphino)ethane and 1,3-bis(diphenylphosphino)propane and with 2,2'-bipyridine (L±L) which gives the complexes (g 1 -C 3 H 5 )Re-(CO) 3 (L±L). By reaction of (g 3 -C 3 H 5 )Re(CO) 4 with bis(diphenylphosphino)methane the allyl group is protonated and under elemination of propene the complex (OC) 3 Re(Ph 2 PCHPPh 2 )(g 1 -Ph 2 PCH 2 PPh 2 ) (19) with a di-phosphinomethanide ligand is formed. On heating solutions of (g 3 -C 3 H 5 )Re(CO) 4 and (g 3 -C 3 H 5 )Re(CO) 3 (CN-2,5-Me 2 C 6 H 3 ) (5) in methanol the methoxy bridged compounds Re 4 (CO) 12 (OH)(OMe) 3 and Re 2 (CO) 4 (CN-2,5-Me 2 C 6 H 3 ) 4 -(l-OMe) 2 (20) were isolated. The crystal structures of (g 3 -C 3 H 5 )Re(CO) 3 (CNCH 2 SiMe 3 ) (4), [(g 3 -C 3 H 5 )(OC) 3 Re] 2 -(l-bis-(diphenylphosphino)ferrocene) (8), (g 1 -C 3 H 5 )Re(CO) 3 -(bpy) (14), of 19, 20 and of (OC) 3 Re-[Ph 2 P(CH 2 ) 3 PPh 2 ]Cl (16) were determined by X-ray diffraction.