Platinum,iridium and rhodium complexes with substituted bis-(diphenylphosphino)methane ligands Ph2PCH(R)PPh2 (R = Me,Ph or SiMe3) |
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| Authors: | Al-Hayaly Lamaan J |
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| Institution: | (1) Department of Chemistry, College of Education for Women, University of Tikrit, Tikrit, Iraq |
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| Abstract: | Substituted phosphines of the type Ph2PCH(R)PPh2 and their PtII complexes PtX2{Ph2PCH(R)PPh2}] (R = Me, Ph or SiMe3; X = halide) were prepared. Treatment of PtCl2(NCBut)2] with Ph2PCH(SiMe3)-PPh2 gave PtCl2(Ph2PCH2PPh2)], while treatment with Ph2PCH(Ph)PPh2 gave Pt{Ph2PCH(Ph)PPh2}2]Cl2. Reaction of p-MeC6H4C≡CLi or PhC≡CLi with PtX2{Ph2PCH(Me)PPh2}] gave Pt(C≡CC6H4Me-p)2-{Ph2PCH(Me)PPh2}] (X = I) and Pt{Ph2PC(Me)PPh2}2](X = Cl),while reaction of p-MeC6H4C≡CLi with Pt{Ph2PCH(Ph)PPh2}2]Cl2 gave Pt{Ph2PC(Ph)PPh2}2]. The platinum complexes PtMe2(dpmMe)] or Pt(CH2)4(dpmMe)] fail to undergo ring-opening on treatment with one equivalent of dpmMe dpmMe = Ph2PCH(Me)PPh2]. Treatment of Ir(CO)Cl(PPh3)2] with two equivalents of dpmMe gave Ir(CO)(dpmMe)2]Cl. The PF6 salt was also prepared. Treatment of Ir(CO)(dpmMe)2]Cl with Cu(C≡CPh)2], AgCl(PPh3)] or AuCl(PPh3)] failed to give heterobimetallic complexes. Attempts to prepare the dinuclear rhodium complex Rh2(CO)3(μ-Cl)(dpmMe)2]BPh4 using a procedure similar to that employed for an analogous dpm (dpm = Ph2PCH2PPh2) complex were unsuccessful. Instead, the mononuclear complex Rh(CO)(dpmMe)2]BPh4 was obtained. The corresponding chloride and PF6 salts were also prepared. Attempts to prepare Rh(CO)(dpmMe)2]Cl in CHCl3 gave RhHCl(dpmMe)2]Cl. Recrystallization of Rh(CO)(dpmMe)2]BPh4 from CHCl3/EtOH gave RhO2(dpmMe)2]BPh4. Treatment of Rh(CO)2Cl2]2 with one equivalent of dpmMe per Rh atom gave two compounds, Rh(CO)(dpmMe)2]Cl and a dinuclear complex that undergoes exchange at room temperature between two formulae: Rh2(CO)2(μ-Cl)(μ-CO)(dpmMe)2]Cl and Rh2(CO)2-(μ-Cl)(dpmMe)2]Cl.
This revised version was published online in June 2006 with corrections to the Cover Date. |
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