Gallium/Group 15 Heterocycles Derived from a Bis(gallylene)

Reaction of the bis(gallylene) 1 with azobenzene and the triphosphirane (PMes) 3 gives rise to the bis(spirocycle) 2 and the 1,2‐diphospha‐3,4‐digalletane 4 , respectively. These findings highlight the ambident reactivity of the bis(gallylene) as its two low‐valent gallium centers react individually in the first case, while the cooperation of both metal centers is necessary in the second case. Both reaction products have been fully characterized, including single‐crystal X‐ray diffraction analysis as well as NMR and IR spectroscopy. Remarkably, when 2 is dissolved in acetonitrile, tautomerism along with rearomatization is observed, thereby affording 3 as evidenced by single‐crystal X‐ray diffraction analysis.