Monosubstituted Doublet Sn(I) Radical Featuring Substantial Unquenched Orbital Angular Momentum

Due to their intrinsic high reactivity, isolation of heavier analogues of carbynes remains a great challenge. Here, we report the synthesis and characterization of a neutral monosubstituted Sn­(I) radical (2) supported by a sterically hindered hydrindacene ligand, which represents the first tin analogue of a free carbyne. Different from all Sn­(I/III) species reported thus far, the presence of a sole Sn–C σ bond in 2 renders the remaining two Sn 5p orbitals energetically almost degenerate, of which one is singly occupied and the other is empty. Consequently, its S = 1/2 ground state possesses two-fold orbital pseudo-degeneracy and substantial unquenched orbital angular momentum, as evidenced by one component of its g matrix (1.957, 1.896, and 1.578) being considerably less than 2. Consistent with this unique electronic structure, 2 can bind to an N-heterocyclic carbene to afford a neutral two-coordinate Sn­(I) radical and initiate a one-electron transfer to benzophenone to furnish a Sn­(II)-ketyl radical anion adduct. As a manifestation of its Sn-centered radical nature, 2 reacts with diphenyl diselenide and p-benzoquinone to form Sn–S and Sn–O bonds, respectively.