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Abstract The 1 : 2 reaction of the imidazole‐based dithiolate (
2 ) with GeCl2 • dioxane in THF/TMEDA gives3 , a TMEDA‐complexed dithiolene‐based germylene. Compound3 is converted to monothiolate‐complexed (5 ) and N‐heterocyclic carbene‐complexed (7 ) germanium(II) dithiolene complexes via Lewis base ligand exchange. A bis‐dithiolene‐based germylene (8 ), involving a 3c–4e S‐Ge‐S bond, has also been synthesized through controlled hydrolysis of7 . The bonding nature of3 ,5 , and8 was investigated by both experimental and theoretical methods. -
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
