Accessing cationic tetrylene-nickel(0) systems featuring donor-acceptor E-Ni triple bonds (E = Ge, Sn)

Philip M Keil; Terrance J Hadlington

doi:10.1039/d2cc00422d

Accessing cationic tetrylene-nickel(0) systems featuring donor-acceptor E-Ni triple bonds (E = Ge, Sn)

Chem Commun (Camb). 2022 Mar 1;58(18):3011-3014. doi: 10.1039/d2cc00422d.

Authors

Philip M Keil¹, Terrance J Hadlington¹

Affiliation

¹ Fakultät für Chemie, Technische Universität München, Lichtenbergstraße 4, Garching 85747, Germany. terrance.hadlington@tum.de.

PMID: 35147635
DOI: 10.1039/d2cc00422d

Abstract

We describe facile synthetic methods for accessing linear cationic tetrylene nickel(0) complexes [^SiiPDippE·Ni(PPh₃)₃]⁺ (E = Ge (4) and Sn (5); ^SiiPDipp = [(iPr₃Si)(Dipp)N]^-), which feature donor-acceptor E-Ni triple bonds. These species are readily accessed in a one-pot protocol, combining the bulky halo-tetrylenes ^SiiPDippECl (E = Ge (1) and Sn (2)), Ni(cod)₂, PPh₃, and Na[BAr^F₄]. Given the diamagnetic nature of 4 and 5, they each contain a formal zero-valent Ni centre, making the E-M triple bonds in these complexes unique compared to previously reported metal tetrylidyne complexes, which typically feature covalent/ionic bonding. In-depth computational analyses of these species further support triple bond character in their E-Ni interactions.