The new water-soluble ligand dmPTA(OSO(2)CF(3))(2) (1) (dmPTA = N,N'-dimethyl-1,3,5-triaza-7-phosphaadamantane) has been synthesized by reaction of PTA with MeOSO(2)CF(3) in acetone (PTA = 1,3,5-triaza-7-phosphatricycle[3.3.1.1(3,7)]decane). The reaction of 1 with KOH gave rise to the new water-soluble ligand dmoPTA (3) (dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) by elimination of the -CH(2)- group located between both NCH(3) units. Compound dmPTA(BF(4))(2) (2) and complex [RuClCp(HdmoPTA)(PPh(3))](OSO(2)CF(3)) (4) have also been synthesized, while compounds HdmoPTA(BF(4)) (3a) and [RuClCp(dmPTA)(PPh(3))](OSO(2)CF(3)) (5) were characterized but not isolated. The new ligands and the complex have been fully characterized by NMR, IR, elemental analysis, and X-ray crystal structure determination (ligand 1 and complex 4). The synthetic processes for 3 and 4 were studied.
The new water soluble complexes [RuClCp(HPTA)2]Cl2·2H2O (2), [RuCp(DMSO-κS)(PTA)2]Cl (3), [RuCp(DMSO-κS)(PTA)2](OSO2CF3) (4) and [RuCp(DMSO-κS)(HPTA)2]Cl3·2H2O (5) have been synthesized and fully characterized by NMR, IR and elemental analysis. The structures of complexes 2·2H2O and 5·2H2O were also characterized by single crystal X-ray determination. The catalytic activity of the complexes and [RuClCp(PTA)2] () for the isomerisation in water of 1-octen- to 1-penten-3-ol was assessed and discussed.
The dinuclear complex [RuClCp(PPh3)-mu-dmoPTA-1kappa P:2kappa(2)N, N'-Co(acac-kappa(2)O, O') 2].H 2O (2; dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) has been synthesized by reaction of [RuClCp(HdmoPTA)(PPh3)](OSO2CF3) (1) with Co(acac)2 in methanol (HdmoPTA = 3,7-H-3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane). Elemental analysis, IR, NMR, and single-crystal X-ray structure determination have characterized the new complex. This complex is active for the catalytic isomerization of but-1-en-3-ol in acetone better than 1.
Graphical AbstractIsomerization in presence of water under Ar and air of 1-octen-3-ol, 1-hepten-3-ol and 1-hexen-3-ol canalized by Ru (1) and Ru-M (M = Ni (2), Co (3), Zn (4)) complexes containing the ligand dmoPTA was investigated.
*Graphical Abstract
Highlights-Homogeneous catalytic isomerization of allylic-alcohols in presence of water.-Ru complexes containing the open adamantane phosphine dmoPTA.-Bi-heterometallic-Ru-M complexes (M = Co, Ni, Zn) containing dmoPTA.-Water and pH influence on the catalytic isomerization of allylic-alcohols.
*Highlights (for review)Evaluation of catalytic activity of [RuClCp(dmoPTA) for the isomerization of 1-octen-3-ol.
The synthesis of novel heterobimetallic derivatives of general formula [RuClCp(PPh(3))-μ-dmoPTA-1κP:2κ(2)N,N'-M(acac-κ(2)O,O')(2)] (M = Ni (3), Zn (4); dmoPTA = 3,7-dimethyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) is described. The preparations of the ruthenium-cobalt analogue (M = Co (2)) and the starting compound [RuClCp(HdmoPTA-κP)(PPh(3))](CF(3)SO(3)) have been revised and their yield improved. Similar to 2, the solid state structures of 3 and 4 show that the dmoPTA-P and the dmoPTA-N(CH(3)) atoms are involved in the coordination to the {RuCpCl(PPh(3))} and {M(acac)(2)} moieties, respectively. The size of the diffusing units is almost the same for the three binuclear complexes, indicating that they exhibit similar solution structures. The diamagnetic ruthenium-zinc derivative was fully characterized in solution at 193 K by NMR as two diastereomeric pairs of enantiomers (R-Ru, Δ-Zn; R-Ru, Λ-Zn; S-Ru, Δ-Zn; S-Ru, Λ-Zn). Finally, the electrochemical properties of the complexes have been investigated by cyclic voltammetry.
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