Se(C 5 F 4 N) 2 and Te(C 5 F 4 N) 2 were prepared via redox transmetalations of AgC 5 F 4 N and the corresponding elements in good yields. The crystal structures of both derivatives exhibit infinite chains caused by a weak intermolecular contact between the chalcogen and one nitrogen atom with a T-shaped (ψ-pentagonal-bipyramidal) ligand arrangement. Crystallization of both reagents from dimethylsulfoxide gave single crystals of the corresponding 1:1 adducts that crystallize in infinite chains best expressed by the formula [E(C 5 F 4 N) 2 •(μ-DMSO)] ∞ (E = Se, Te). In these cases, the coordination spheres of selenium and tellurium are square-planar (ψ-octahedral). Similar effects are found in the molecular structures of [Te(C 5 F 4 N) 2 •TMTU] ∞ and [Te(C 6 F 5 ) 2 •TMTU] ∞ (TMTU = tetramethylthiourea). Differences in the Te−S interatomic distances clearly indicate the C 5 F 4 N ligand being significantly more electron-withdrawing in comparison with the C 6 F 5 group; that is, Te(C 5 F 4 N) 2 is the stronger Lewis acid. a Values may be interchangeable. b Not measured. Article pubs.acs.org/Organometallics
The reactions of H2C[C(Me)N(C6H3‐2, 6‐i‐Pr2)]2 ((DPP)2NacNacH) and Zn(C6F5)2 · 2 EtCN or Cd(C6F5)2 · 2 MeCN in a molar ratio of approximately 1:1 selectively gave the derivatives (DPP)2NacNacMC6F5 (M = Zn, Cd) in excellent yields. No reaction was observed between (DPP)2NacNacH and Hg(C6F5)2 under similar conditions. Reactions with Hg(C6F5)OCOMe yielded the products of dismutation, Hg(C6F5)2 and Hg(OCOMe)2. (DPP)2NacNacZnC6F5 crystallises as a 1:1 adduct with THF with two independent molecules per unit cell (triclinic, P1 (no. 2)). The zinc atom is tetrahedrally surrounded by the chelating ligand, the pentafluorophenyl group and one THF molecule. A similar situation is found in the 1:1 adduct of (DPP)2NacNacCdC6F5 and DMF (monoclinic, P21/n (no. 14)), while in the donor‐free compound (CDCl3 and H2O co‐crystallize) the cadmium atom is nearly ideally trigonal planar co‐ordinated (orthorhombic, Pbnm (no. 62)).
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