Unsymmetrical Linear Pentanuclear Nickel String Complexes: [Ni<sub>5</sub>(tpda)<sub>4</sub>(H<sub>2</sub>O)(BF<sub>4</sub>)](BF<sub>4</sub>)<sub>2</sub> and [Ni<sub>5</sub>(tpda)<sub>4</sub>(SO<sub>3</sub>CF<sub>3</sub>)<sub>2</sub>](SO<sub>3</sub>CF<sub>3</sub>)
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The one-electron oxidized linear pentanuclear nickel complexes [Ni5(tpda)4(H2O)(BF4)](BF4)2 (1) and [Ni5(tpda)4(SO3CF3)2](SO3CF3) (2) have been synthesized by reacting the neutral compound [Ni5(tpda)4Cl2] with the corresponding silver salts. These compounds have been characterized by various spectroscopic techniques. Compound 1 crystallizes in the monoclinic space group P21/n with a = 15.3022(1) Å, b = 31.0705(3) Å, c = 15.8109(2) Å, β = 92.2425(4)°, V = 7511.49(13) Å3, Z = 4, and compound 2 crystallizes in the monoclinic space group C2/c with a = 42.1894(7) Å, b = 17.0770(3) Å, c = 21.2117(4) Å, β = 102.5688(8)°, V = 14916.1(5) Å3, Z = 8. X-ray structural studies reveal an unsymmetrical Ni5 unit for both compounds 1 and 2. Compounds 1 and 2 show stronger Ni−Ni interactions as compared to those of the neutral compounds.
