Highly Unsaturated Platinum and Palladium Carbenes PtC₃ and PdC₃ Isolated and Characterized in the Gas Phase

Abstract

Carbenes of platinum and palladium, PtC3 and PdC3, were generated in the gas phase through laser vaporization of a metal target in the presence of a low concentration of a hydrocarbon precursor undergoing supersonic expansion. Rotational spectroscopy and ab initio calculations confirm that both molecules are linear. The geometry of PtC3 was accurately determined by fitting to the experimental moments of inertia of twenty‐six isotopologues. The results are consistent with the proposal of an autogenic isolobal relationship between O, Au+, and Pt atoms.

Sensing Chirality with Rotational Spectroscopy

“…With the extension to the millimetre range, (29) laboratory broadband measurements can also be combined with radio-telescope observations for the assignment of chemical species in the interstellar medium. (30) Additionally, metal complexes, (31,32) plasmas, (33) flash pyrolysis reaction intermediates, (34) and Rydberg transitions (35) have also been investigated using CP-FTMW spectroscopy.…”

Isoelectronic IrC3–, PtC3, and AuC3+ Clusters Featuring the Structural and Bonding Resemblance to OC3

“…Since Ir – , Pt, and Au + have the same number of electrons, we assume that Ir – may have similar chemical properties to those of the Pt and Au + . Previous studies have indicated that PtC 3 and AuC 3 + are linear structures with an MCCC characteristic. , To verify our assumption, photoelectron spectra and quantum calculations are performed to study the MC 3 – (M = Ir and Pt) clusters. We find that IrC 3 – and PtC 3 have structures that are similar to those of AuC 3 + and OC 3 .…”

“…The Pt 3 C + cluster ion has been observed by infrared multiple photon dissociation (IRMPD) spectroscopy, whose geometry was similar to that of the carbonate ion, consistent with the empirical model predictions. In addition, the similarity between PtC 3 and OC 3 has been also proved by rotational spectroscopy . Previous theoretical calculations have revealed analogies between the behavior of each of Au + and Pt and O atom .…”

“…The empirical model has been proposed by Pyykkö et al, where they provided a reasonable chemical basis for the stability of PtC 3 . , There are striking similarities between the geometries of PtC 3 and that reported earlier for OC 3 . Interestingly, platinum can be regarded as the isoelectronic and equivalent counterpart of chalcogens in PtC 3 , which can be used to predict structural and reactivity trends.…”

“…Similarly, the NbC n – ( n = 2–7) clusters were identified to have C 2 v cyclic structures. But for the PtC 3 and PdC 3 clusters, the linear isomers were found to be more stable, , and RhC 3 was also the same structure with PtC 3 and PdC 3 . An experimental study of AuC n + revealed that the mass spectrum of AuC 3 + had a relatively high ion intensity, and the linear isomer was found to be more stable .…”