An Open-Shell Singlet SnI Diradical and H2 Splitting.

The first SnI diradical [(ADCPh )Sn]2 (4) based on an anionic dicarbene (ADCPh ={CN(Dipp)}2 CPh; Dipp=2,6-iPr2 C6 H3 ) scaffold has been isolated as a green crystalline solid by KC8 reduction of the corresponding bis-chlorostannylene [(ADCPh )SnCl]2 (3). The six-membered C4 Sn2 -ring of 4 containing six π-electrons shows a diatropic ring current, thus 4 may also be regarded as the first 1,4-distannabenzene derivative. DFT calculations suggest an open-shell singlet (OS) ground state of 4 with a remarkably small singlet-triplet energy gap (ΔEOS-T =4.4 kcal mol-1 ), which is consistent with CASSCF (ΔES-T =6.6 kcal mol-1 and diradical character y=37 %) calculations. The diradical 4 splits H2 at room temperature to yield the bis-hydridostannylene [(ADCPh )SnH]2 (5). Further reactivity of 4 has been studied with PhSeSePh and MeOTf.