Tsuno, Takashi and Sugiyama, Yu and Brunner, Henri and Bodensteiner, Michael and Lee, Kosei (2017) Synthesis and structural characterization of Ni(II) complexes with the chiral CpH(PNMent) tripod ligand. JOURNAL OF COORDINATION CHEMISTRY, 70 (20). pp. 3459-3470. ISSN 0095-8972, 1029-0389
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Treatment of NiCl2 with the tripod ligand (L-Ment, S-C)-1H led to (L-Ment, S-C)-[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 [(L-Ment, S-C)[Cp(PNMent) NiCl] readily underwent Cl/PPh3 exchange to give (L-Ment, S-C)-[Cp(PNMent) NiPPh3] PF6. Reaction of (L-Ment, S-C)-[Cp(PNMent) NiCl] with 0.5 eq. of dppe afforded [{(L-Ment, S-C)-[Cp(PNMent) Ni]}(2) dppe](PF6)(2). (L-Ment, S-C)-[Cp(PNMent) NiPPh3] PF6 and [{(L-Ment, S-C)-[Cp(PNMent) Ni]}(2) dppe] (PF6)(2) were characterized by NMR and MS spectroscopy, and also by single crystal X-ray diffraction. The cyclopentadienyl ligand of (L-Ment, S-C)[Cp(PNMent) NiPPh3] PF6 shows a distortion intermediate between the ene-allyl and diene types, while the two cyclopentadienyl ligands of [{(L-Ment, S-C)-[Cp(PNMent) Ni]}(2) dppe](PF6)(2) have intermediate and diene distortions, respectively. According to the temperature dependent NMR spectra of (L-Ment, S-C)-[Cp(PNMent) NiPPh3] PF6 and [{(L-Ment, S-C)[Cp(PNMent) Ni]}(2) dppe](PF6)(2) two different conformations of the tether in the Cp(PNMent) Ni system could be frozen out at low temperatures. [GRAPHICS] .
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | LABILE METAL CONFIGURATION; NICKEL NHC COMPLEXES; CRYSTAL-STRUCTURES; CYCLOPENTADIENYL; STABILIZATION; ELECTROCHEMISTRY; POLYMERIZATION; DERIVATIVES; ALKYNYL; RING; Ni(II) complexes; Chiral-at-metal complexes; Tridentate ligand; Crystal structure |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 14 Dec 2018 13:01 |
| Last Modified: | 20 Feb 2019 14:04 |
| URI: | https://pred.uni-regensburg.de/id/eprint/608 |
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