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The reaction of two equivalents of LiC6H3‐2,6‐(C6H3‐2,6‐Pri2)2 with GeCl2·dioxane, SnCl2 or PbBr2 in a diethyl ether solution resulted in the isolation of the monomeric σ‐bonded diaryl tetrylene series E{C6H3‐2,6‐(C6H3‐2,6‐Pri2)2}2 (E = Ge ( 1 ), Sn ( 2 ), or Pb( 3 )). Compounds 1 ‐ 3 are highly sterically congested blue crystalline solids, which possess V‐shaped structures and wide interligand bond angles. The solid state structures of 1 ‐ 3 were determined by single‐crystal X‐ray methods while their solution structures were investigated by UV spectroscopy and in the cases of 2 and 3 , respectively, by 119Sn and 207Pb NMR spectroscopy. The series 1 ‐ 3 constitutes the most sterically crowded examples of σ‐bonded diorgano group 14 derivatives yet isolated and, in contrast to previously reported: ER2 species, the C‐E‐C angles increase with increasing atomic number. 相似文献