Unravelling carbene moiety role in the N-heterocyclic carbene-phosphinidenes coordination chemistry: bonding and reactivity in gold chemistry

Abstract

The coordination properties of the emerging class of N-heterocyclic carbene-phosphinidene (NHCP) ligands have been reported to be strongly affected by the carbene (NHC) moiety, but a clear understanding remains strikingly limited. In this work the bonding features and reactivity of 13 NHCP gold hydride complexes, [NHCPAuH], bearing different classes of NHCs have been systematically explored and compared to carbene analogues, using an unbiased computational protocol. The analyses reveal that, although the $\pi$-acceptor ability trend of NHCPs qualitatively parallels that of NHCs, the $\sigma$-donor ability trend reverses, with more $\sigma$-donating NHC moieties generating less $\sigma$-donating NHCP ligands. Concurrently, the nature of the NHC moiety impacts the coordination geometry at the P center, with the CNHC-P-Au bond angle appearing as a structural descriptor to monitor and/or design NHCP ligands with desired $\sigma$-donor properties. The NHCPs stronger $\sigma$-donor and weaker $\pi$-acceptor abilities compared to NHCs and their unique structural flexibility and electronic adaptability have been showcased to be directly controlled by the carbene moiety via modulation of the HOMO lone pair energy and its atomic phosphorous 3p character. The reactivity of [NHCPAuH] complexes with CO2, taken as a probe for potential NHCP applications in small molecule activation processes, demonstrates qualitatively similar mechanisms, with remarkably different activation barriers, which directly correlate with the NHCPs $\sigma$-donor ability, thus reflecting the high tunability of their bonding properties. This work provides insights and perspectives on the design principle of NHCP ligands, with a spotlight on the pivotal role of NHC moiety in modulating their electronic and steric properties, offering opportunities for burgeoning applications across diverse fields.