Small silicon hydrides have attracted extensive interest because of their role in the chemical evolution of circumstellar envelopes of evolved carbon stars and applications in surface growth processes and as transients in semiconductor manufacturing. Combined with electronic structure calculations, we demonstrate that monobridged silylidynesilylenes [(Si(μ-D)SiH 2 , Si(μ-H)SiHD, Si(μ-H)SiH 2 ] and silylsilylidyne [H 3 SiSi, H 2 DSiSi], which are nearly isoenergetic, can be prepared via molecular hydrogen loss channels in the crossed molecular beam study of the reaction of D1-silylidyne (SiD; X 2 Π) with silane (SiH 4 ; X 1 A 1 ) in a crossed molecular beams machine. Compared to the dynamics of the isovalent methylidyne (CH) − methane (CH 4 ) system, our study delivers a unique view at the intriguing isomerization processes and reaction dynamics of dinuclear silicon hydride transients, thus contributing to our knowledge on the chemical bonding of silicon hydrides at the molecular level.