Bridged and Unbridged Nickel-Nickel Bonds Supported by Cyclopentadienyl and Phosphine Ligand-Sets

Peter Cleaves, Alexander J. Ayres, Lisa Vondung, John C. Stewart, Philip Cobb, Ashley Wooles, Stephen Liddle

Research output: Contribution to journalArticlepeer-review


A series of Ni complexes [Ni(Cl)2(PR3)2] with R = Me (1-Me), nPr (1-nPr) and n Bu (1-nBu) and nickelocenes [Ni(η5 -C5H4R′)2] with R′ = H (2-H), Me (2-Me), SiMe3 (2-SiMe3) were synthesized and characterized. From these complexes, the synthesis of the Ni complexes [NiCl(PR3)(η5-C5H4R′)] R = Me, R′ = H (3-Me), R= n Bu, R′ = H (3- nBu), R =n Pr, R′ = H (3- nPr), R = Et, R′ = Me (4) and R = Et, R′ = SiMe3 (5) was achieved. All complexes were fully characterized, including single crystal X-ray crystallography. Complexes 3-R, 4 and 5 were then used to obtain homobimetallic Ni complexes with rare examples of unbridged Ni-Ni bonds [{Ni(η5 -C5H5)(PR3)}2], with R = Me (7-Me) and R = n Pr (7- nPr) being structurally characterized by single crystal X-ray diffraction. In order to probe the effect of bridging ligands on the Ni-Ni bond, the bridged complex [{Ni(µ:η5 -C5H4CH2CH2P(t Bu)2}2] (8) was synthesized from the monomeric precursor [Ni(Cl)(k1 -η5 -C5H4CH2CH2Pt Bu2)] (6). The Ni-Ni distances in 7-Me, 7- nPr, and 8 were found to be 2.407(1), 2.3931(6), and 2.6027(17) Å, respectively, the latter seemingly lengthened compared to the other two due to the tethered nature of the bridging ligand. DFT calculations confirm the presence of unbridged σ-bonds between the Ni-atoms in 7-Me and 7-nPr and show that the bridging ligand in 8 has a minimal effect on the character of the Ni-Ni bond.
Original languageEnglish
Publication statusAccepted/In press - 9 Nov 2020


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