Directed gas-phase preparation of the elusive phosphinosilylidyne (SiPH, XA'') and cis/trans phosphinidenesilyl (HSiPH; XA') radicals under single-collision conditions.

The reaction of the D1-silylidyne radical (SiD; XΠ) with phosphine (PH; XA) was conducted in a crossed molecular beams machine under single collision conditions. Merging of the experimental results with ab initio electronic structure and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations indicates that the reaction is initiated by the barrierless formation of a van der Waals complex (i0) as well as intermediate (i1) formed via the barrierless addition of the SiD radical with its silicon atom to the non-bonding electron pair of phosphorus of the phosphine. Hydrogen shifts from the phosphorous atom to the adjacent silicon atom yield intermediates i2a, i2b, i3; unimolecular decomposition of these intermediates leads eventually to the formation of trans/cis-phosphinidenesilyl (HSiPH, p2/p4) and phosphinosilylidyne (SiPH, p3) via hydrogen deuteride (HD) loss (experiment: 80 ± 11%, RRKM: 68.7%) and d-trans/cis-phosphinidenesilyl (DSiPH, p2'/p4') plus molecular hydrogen (H) (experiment: 20 ± 7%, RRKM: 31.3%) through indirect scattering dynamics via tight exit transition states. Overall, the study reveals branching ratios of p2/p4/p2'/p4' (trans/cis HSiPH/DSiPH) to p3 (SiPH) of close to 4 : 1. The present study sheds light on the complex reaction dynamics of the silicon and phosphorous systems involving multiple atomic hydrogen migrations and tight exit transition states, thus opening up a versatile path to access the previously elusive phosphinidenesilyl and phosphinosilylidyne doublet radicals, which represent potential targets of future astronomical searches toward cold molecular clouds (TMC-1), star forming regions (Sgr(B2)), and circumstellar envelopes of carbon rich stars (IRC + 10216).