Abstract Trisilane 7 has been synthesized as a potential photochemical precursor of tetra- tert-butylsilatetrahedrane (5) and/or tetra-tert-butylsilacyclobutadiene (6). Astonishingly, only one Si, Si bond is broken upon irradiation of 7 and the silacyclobutenyl radical 9 can be identified as the reaction product. The structure of radical 9, which in the absence of oxygen is persistent even at room temperature, has been elucidated by comparison of its ...