Zur oxidativen Addition von 1-Halogenalk-1-inen – Synthese und Struktur von Phenylalkinylpalladium-Komplexen

✍ Scribed by Michael Weigelt; Diana Becher; Eike Poetsch; Clemens Bruhn; Dirk Steinborn

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: German
• Weight: 122 KB
• Volume: 625
• Category: Article
• ISSN: 0372-7874
• DOI: 10.1002/(sici)1521-3749(199909)625:9<1542::aid-zaac1542>3.0.co;2-9

✦ Synopsis

Inhaltsu È bersicht. [Pd(PPh 3 ) 4 ] (2) setzt sich mit ICºCPh und ClCºCPh im Sinne einer oxidativen Addition zu trans-[Pd(CºCPh)X(PPh 3 ) 2 ] (X = I: 3 a, X = Cl: 3 b) um. Als Nebenprodukte werden trans-[PdX 2 (PPh 3 ) 2 ] (X = I: 4 a, X = Cl: 4 b; < 10%) und PhCºC±CºCPh (5; X = I: ca. 30%, X = Cl: < 4%) gebildet. 3 a und 3 b sind NMR-( 1 H, 13 C, 31 P) und IR-spektroskopisch sowie durch Ro È ntgeneinkristallstrukturanalyse charakterisiert. In den Kristallen von 3 a und 3 b liegen isolierte Moleku È le vor. Die Pd±CºC±Ph-Einheit ist in 3 a linear und in 3 b anna È hernd linear [Pd±CºC 174.2(6)°, CºC±C 179,0(7)°]. On the Oxidative Addition of 1-Halogenalk-1-ynes ± Synthesis and Structure of Phenylalkynylpalladium Complexes Abstract. [Pd(PPh 3 ) 4 ] (2) reacts with ICºCPh and ClCºCPh in the sense of an oxidative addition to give trans-[Pd(CºCPh)X(PPh 3 ) 2 ] (X = I: 3 a, X = Cl: 3 b). As side products trans-[PdX 2 (PPh 3 ) 2 ] (X = I: 4 a, X = Cl: 4 b; < 10%) and PhCºC±CºCPh (5; X = I: ca 30%, X = Cl: < 4%) are formed. 3 a and 3 b were characterized by NMR ( 1 H, 13 C, 31 P) and IR spectroscopies as well as by X-ray single-crystal structure analyses. In the crystals of 3 a and 3 b isolated molecules were found. The Pd±CºC±Ph unit is linear in 3 a and approximately linear in 3 b [Pd±CºC 174.2(6)°, CºC±C 179,0(7)°].