Synthesis and structural characterization of Ni(II) complexes with the chiral CpH(PNMent) tripod ligand. Issue 20 (18th October 2017)

• Record Type: Journal Article
• Authors: Tsuno, Takashi; Sugiyama, Yu; Brunner, Henri; Bodensteiner, Michael; Lee, Kosei
• Is Part Of: Journal of coordination chemistry. Volume 70:Issue 20(2017)
• Page Start: 3459
• Page End: 3470
• Publication Date: 2017-10-18
• Subjects: Ni(II) complexes -- Chiral-at-metal complexes -- Tridentate ligand -- Crystal structure; Coordination compounds -- Periodicals; 541.2242
• DOI: 10.1080/00958972.2017.1390222
• Languages: English
• ISSNs: 0095-8972

Abstract

Abstract: Treatment of NiCl2 with the tripod ligand (LMent, S C )-1 H led to (LMent, 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 NH4 PF6 [(LMent, S C )-[Cp(PNMent )NiCl] readily underwent Cl/PPh3 exchange to give (LMent, S C )-[Cp(PNMent )NiPPh3 ]PF6 . Reaction of (LMent, S C )-[Cp(PNMent )NiCl] with 0.5 eq. of dppe afforded [{(LMent, S C )-[Cp(PNMent )Ni]}2 dppe](PF6 )2 . (LMent, S C )-[Cp(PNMent )NiPPh3 ]PF6 and [{(LMent, 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 (LMent, S C )-[Cp(PNMent )NiPPh3 ]PF6 shows a distortion intermediate between the ene-allyl and diene types, while the two cyclopentadienyl ligands of [{(LMent, S C )-[Cp(PNMent )Ni]}2 dppe](PF6 )2 have intermediate and diene distortions, respectively. According to the temperature dependent NMR spectra of (LMent, S C )-[Cp(PNMent )NiPPh3 ]PF6 and [{(LMent, 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. Abstract :