Synthesis and structural characterization of Ni(II) complexes with the chiral CpH(PNMent) tripod ligand |
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| Authors: | Takashi Tsuno Yu Sugiyama Henri Brunner Michael Bodensteiner Kosei Lee |
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| Affiliation: | 1. Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba, Japantsuno.takashi@nihon-u.ac.jp;3. Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba, Japan;4. Institut für Anorganische Chemie, Universit?t Regensburg, Regensburg, Germany |
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| Abstract: | Treatment of NiCl2 with the tripod ligand (LMent,SC)-1H led to (LMent,SC)-[Cp(PNMent)NiCl] in which the potentially tridentate ligand coordinated to the metal center in a bidentate way via the cyclopentadienyl system and the phosphorus atom. In the presence of NH4PF6 [(LMent,SC)-[Cp(PNMent)NiCl] readily underwent Cl/PPh3 exchange to give (LMent,SC)-[Cp(PNMent)NiPPh3]PF6. Reaction of (LMent,SC)-[Cp(PNMent)NiCl] with 0.5 eq. of dppe afforded [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2. (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 and [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 were characterized by NMR and MS spectroscopy, and also by single crystal X-ray diffraction. The cyclopentadienyl ligand of (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 shows a distortion intermediate between the ene-allyl and diene types, while the two cyclopentadienyl ligands of [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 have intermediate and diene distortions, respectively. According to the temperature dependent NMR spectra of (LMent,SC)-[Cp(PNMent)NiPPh3]PF6 and [{(LMent,SC)-[Cp(PNMent)Ni]}2dppe](PF6)2 two different conformations of the tether in the Cp(PNMent)Ni system could be frozen out at low temperatures. |
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| Keywords: | Ni(II) complexes Chiral-at-metal complexes Tridentate ligand Crystal structure |
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