Alternativ‐Liganden. XXIII. Rhodium(I)‐Komplexe mit Donor/Akzeptor‐Liganden des Typs (Me2PCH2CH2SiX2 und (2‐Me2PC6H4)SiXMe2 (X = F, Cl)

TLDR: In this article, a number of ligands of the type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) were characterized by analytical (C, H) and spectroscopic investigations (MS, IR, NMR) charakterisiert.

Abstract: Donor/Akzeptor-Liganden des Typs (Me2PCH2CH2)2SiX2 und (2-Me2PC6H4)SiXMe2 (X = F, Cl) reagieren mit [Rh(CO)2Cl]2 (1) zu den Einkernkomplexen RhCl(CO)(Me2PCH2CH2)2SiX2 [X = F(4), Cl (5)] bzw. RhCl(CO)[(2-Me2PC6H4)SiXMe2]2 [X = F(8), Cl (9)]. Bei den Liganden (Me2PCH2CH2)2SiCl2 (3) und (2-Me2PC6H4)SiCMe2 (7) treten als Folgeprodukte der primar gebildeten Rh(I)-Komplexe durch oxidative Addition von SiCl Rhodium(III)-Verbindungen geringer Loslichkeit auf. Nur im Fall von 8 geben die Koordinationsverschiebungen Δδ = δ(Komplex)−δ(Ligand) und Kopplungskonstanten Hinweise auf mogliche RhSi-Wechselwirkungen. Die durch Rontgenbeugung ermittelte Molekulstruktur von 8 zeigt allerdings keine RhSi- oder RhF-Bindungskontakte. – Die neuen Verbindungen wurden durch analytische (C, H) und spektroskopische Untersuchungen (MS, IR, NMR) charakterisiert. Alternative Ligands. XXIII Rhodium(I) Complexes with Donor/Acceptor Ligands of the Type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) Donor/acceptor ligands of the type (Me2PCH2CH2)2SiX2 and (2-Me2PC6H4)SiXMe2 (X = F, Cl) react with [Rh(CO)2Cl]2 (1) to give the mononuclear complexes RhCl(CO)(Me2PCH2CH2)2SiX2 [X = F(4), Cl (5)] and RhCl(CO)[2-Me2PC6H4)SixMe2]2 [X = F (8), Cl (9)], respectively. In case of the ligands (Me2PCH2CH2)2SiCl2 (3) and (2-Me2PC6H6)SiClMe2 (7) the Rh(I) complexes formed in the first step partly undergo oxidative addition reactions of SiCl bonds yielding rhodium(III) compounds of low solubility. Only for 8 the coordination shifts Δδ = δ(complex)−δ(ligand) and coupling constants give some indication to possible RhSi interactions. However, the molecular structure of 8 determined by X-ray diffraction does not show RhSi or RhF bonding contacts. The new compounds were characterized by analytical (C, H) and spectroscopic investigations (MS, IR,-NMR).