| Abstrakt: |
Reaction of CpIrCl221 with dpmp in the presence of KPF6afforded a binuclear complex CpIrCldpmp-P1,P2;P3IrCl2CpPF62 dpmp Ph2PCH22PPh. The mononuclear complex CpIrCldpmp-P1,P2PF64 was generated by the reaction of CpIrCl2BDMPP BDMPP PPh2,6-MeO2C6H32 with dpmp in the presence of KPF6. These mono- and binuclear complexes have four-membered ring structures with a terminal and a central P atom of the dpmp ligand coordinated to an iridium atom as a bidentate ligand. Since there are two chiral centers at the Ir atom and a central P2atom, there are two diastereomers that were characterized by spectrometry. Complexes anti-4and syn-4reacted with CpRhCl22or C6Me6RuCl22, giving the corresponding mixed-metal complexes, anti- and syn-CpIrCldppm-P1,P2;P3MCl2LPF66: M Rh, L Cp; 7: M Ru, L C6Me6. Treatment with AuClSC4H8 gave tetranuclear complexes, anti- and syn-8CpIrCldppm-P1,P2;P3AuCl2PF62bearing an Au–Au bond. Reaction of anti-4with PtCl2cod generated the trinuclear complex anti-9, anti-CpIrCldppm-P1,P2;P32PtCl2PF62. These reactions proceeded stereospecifically. The P,O-chelated complex syn-CpIrClBDMPP-P,Osyn-10 BDMPP-P,OPPh2,6-MeO2C6H32-O-6-MeOC6H32 reacted with dpmp in the presence of KPF6, generating the corresponding anti-complex as a main product as well as a small amount of syn-complex, CpIrBDMPP-P,Odppm-P1PF611. The reaction proceeded preferentially with inversion. The reaction processes were investigated by PM3 calculation. anti-11was treated with MCl2cod, giving anti-CpIrBDMPP-P,Odppm-P1;P2,P3MCl2PF614: M Pt; 15: M Pd, in which the MCl2moiety coordinated to the two free P atoms of anti-11. The X-ray analyses of syn-2, anti-2, anti-4, anti-8and anti-11were performed. |
