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Award ID contains: 1855641

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  1. Abstract Reaction of carbene‐stabilized disilicon (1) with the lithium‐based dithiolene radical (2.) affords the first dianionic silicon tris(dithiolene) complex (3). Notably, the formation of3represents the unprecedented utilization of carbene‐stabilized disilicon (1) as a silicon‐transfer agent. The nature of3was probed by multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction, and DFT computations. 
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  2. 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. 
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  3. null (Ed.)