The synthesis and characterization of several m-terphenyl heavier main group 15 (P, As, Sb, or Bi) dihalides, together with their reduction to give a homologous series of double-bonded dipnictenes, are reported. Reaction of LiC6H3-2,6-Mes2 (Mes = C6H2-2,4,6-Me3) or LiC6H3-2,6-Trip2 (Trip = C6H2-2,4,6-iPr3) with the appropriate trihalide affords 2,6-Mes2H3C6ECl2 (E = As, 1; Sb, 2; Bi, 3) and 2,6-Trip2H3C6ECl2 (E = P, 4; As, 5; Sb, 6; Bi, 7). The compounds 1 − 7 were characterized by 1H and 13C NMR spectroscopy as well as by 31P NMR spectroscopy in the case of 4. In addition, the structures of 3, 5, and 6 were determined. Reduction of the phosphorus species 4 with potassium in hexane gives a mixture of the diphosphene 2,6-Trip2H3C6PPC6H3-2,6-Trip2, 12, and the phosphafluorene species, 1-(2,4,6-triisopropylphenyl)-5,7-diisopropyl-9-phosphafluorene, 11. The compound 11, which results from the insertion of a phosphorus into a C(Ar)−C(i-Pr) bond was synthesized in higher yield by the reduction of 4 with magnesium. The simple reduction of 1 − 4, 6, and 7 with potassium, and of 5 with magnesium, yielded the new series of dipnictenes, 2,6-Mes2H3C6E=EC6H3-2,6-Mes2 (E = As, 8; Sb, 9; Bi, 10) and 2,6-Trip2H3C6E=EC6H3-2,6-Trip2 (E = P, 12; As, 13; Sb, 14a; Bi, 15), as well as the partially reduced species 2,6-Trip2H3C6(Cl)SbSb(Cl)C6H3-2,6-Trip2 (14b). The compounds, which displayed high thermal stability, were characterized by 1H, 13C, and 31P NMR and UV−vis spectroscopy. The structures of 8 − 11, 13, 14a, and 14b were determined. These compounds constitute the first homologous series of dipnictene structures for all the heavier group 15 elements. The E−E bond shortenings observed for the heaviest antimony or bismuth derivatives lead to the conclusion that π overlap is quite important in the fifth- and sixth-period elements of this group.

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The base-free metallocenes [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Ca, [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Sr, and [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Ba have been prepared by reaction of MI 2 and the sodium or potassium salt of the substituted cyclopentadiene anion in THF, while [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 Mg was prepared from the cyclopentadiene, 1,2,4-(Me 3 C) 3 C 5 H 3 , and dibutylmagnesium. The structures of the magnesocene and calcocene as well as those of the previously prepared ytterbium and samarium analgoues have been determined by X-ray crystallography. The metallocenes are slightly bent in the solid state with centroid-metal-centroid angles ranging from 163°to 173°. Adducts of the strontocene and samarocene with THF and of the barocene, samarocene, and ytterbocene with 2,6-Me 2 C 6 H 3 NC have also been prepared and characterized. The massive bulk of the [1,2,4-(Me 3 C) 3 C 5 H 2 ]ligand leads to behavior quite different from that previously observed for base-free metallocenes of the alkaline earths and divalent lanthanides.