Coordination Chemistry of 2,2‘-Dipyridyl Diselenide: X-ray Crystal Structures of PySeSePy, [Zn(PySeSePy)Cl<sub>2</sub>], [(PySeSePy)Hg(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub>], [Mo(SePy)<sub>2</sub>(CO)<sub>3</sub>], [W(SePy)<sub>2</sub>(CO)<sub>3</sub>], and [Fe(SePy)<sub>2</sub>(CO)<sub>2</sub>] (PySeSePy = C<sub>5</sub>H<sub>4</sub>NSeSeC<sub>5</sub>H<sub>4</sub>N; SePy = [C<sub>5</sub>H<sub>4</sub>N(2-Se)-<i>N,Se</i>])
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The coordination chemistry of 2,2‘-dipyridyl diselenide (PySeSePy) (2) (C10H8N2Se2) has been investigated and its crystal structure has been determined (monoclinic, P21/c, a = 10.129(2) Å, b = 5.7332(12) Å, c = 19.173(3) Å, β = 101.493(8)°, Z = 4). In metal complexes the ligand was found to coordinate in three different modes, as also confirmed by X-ray structure determination. N,N‘-coordination was found in the zinc complex [Zn(PySeSePy)Cl2] (3) (C10H8Cl2N2Se2Zn, triclinic, P1̄, a = 7.9430(10) Å, b = 8.147(2) Å, c = 11.999(2) Å, α = 93.685(10)°, β = 107.763(10)°, γ = 115.440(10)°, Z = 2) and Se,Se‘-coordination in the adduct of the ligand with bis(pentafluorophenyl)mercury(II) [PySeSePyHg(C6F5)2] (5) (C10H8F10HgN2Se2, monoclinic, P21/n, a = 7.7325(10) Å, b = 5.9974(14) Å, c = 25.573, β = 98.037(10)°, Z = 2), which however displays only weak interactions between selenium and mercury. The reaction of the ligand with norbornadiene carbonyl complexes of molybdenum and tungsten leads to reductive cleavage of the selenium−selenium bond with oxidation of the metal center and concomitant addition of the resulting selenolate to the metal carbonyl fragment. Thus the 7-coordinate complexes [Mo(SePy)2(CO)3] (6) (C13H8MoN2O3Se2, monoclinic, P21/n, a = 9.319(3) Å, b = 12.886(5) Å, c = 13.231(6) Å, β = 109.23(3)°, Z = 4) and [W(SePy)2(CO)3] (7) (C13H8N2O3Se2W, monoclinic, P21/n, a = 9.303(2) Å, b = 12.853(2) Å, c = 13.232(2) Å, β = 109.270(10)°, Z = 4) were obtained. The same N,Se-coordination pattern emerges from the reaction of [Fe2(CO)9] with (2) leading to [Fe(SePy)2(CO)2] (8) (C12H8FeN2O2Se2, monoclinic, P1̄, a = 8.6691(14) Å, b = 12.443(2) Å, c = 14.085(2) Å, α = 105.811(10)°, β = 107.533(8)°, γ = 92.075(10)°, Z = 4).
