Reaction of carbene‐stabilized disilicon (
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Abstract 1 ) with the lithium‐based dithiolene radical (2. ) affords the first dianionic silicon tris(dithiolene) complex (3 ). Notably, the formation of3 represents the unprecedented utilization of carbene‐stabilized disilicon (1 ) as a silicon‐transfer agent. The nature of3 was probed by multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction, and DFT computations. -
While the 1 : 1 reaction of 3 with an N-heterocyclic carbene ({(Me)CN(i-Pr)} 2 C:) in THF resulted in ligand-substituted product 4, the corresponding 1 : 2 reaction (in the presence of H 2 O) gives the first structurally characterized germanium tris(dithiolene)dianion 5 as the major product and the “naked” dithiolene radical 6˙ as a minor by-product. The structure and bonding of 4 and 5 were probed by experimental and theoretical methods. Our study suggests that carbene-mediated partial hydrolysis may represent a new method to access tris(dithiolene) complexes of main-group elements.more » « less