Syntheses, Reactivity, and Crystal Structures of Molybdenum Complexes with Pyridine-2-thionate (pyS)-Containing Ligands: Crystal Structures of [Mo(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(CO)<sub>2</sub>]<sub>2</sub>(μ-η<sup>1</sup>,η<sup>2</sup>-pyS)<sub>2</sub>, <i>e</i><i>xo</i>-[Mo(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(CO)(η<sup>2</sup>-pyS)(η<sup>2</sup>-dppe)], [Mo(CO)<sub>3</sub>(η<sup>1</sup>-SC<sub>5</sub>H<sub>4</sub>NH)(η<sup>2</sup>-dppm)], and [Mo(CO)(η<sup>2</sup>-pyS)<sub>2</sub>(η<sup>2</sup>-dppm)]
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The doubly bridged pyridine-2-thionate (pyS) dimolybdenum complex [Mo(η3-C3H5)(CO)2]2(μ-η1,η2-pyS)2 (1) is accessible by the reaction of [Mo(η3-C3H5)(CO)2(CH3CN)2Br] with pySK in methanol at room temperature. Complex 1 reacts with piperidine in acetonitrile to give the complex [Mo(η3-C3H5)(CO)2(η2-pyS)(C5H10NH)] (2). Treatment of 1 with 1,10-phenanthroline (phen) results in the formation of complex [Mo(η3-C3H5)(CO)2(η1-pyS)(phen)] (3), in which the pyS ligand is coordinated to Mo through the sulfur atom. Four conformational isomers, endo,exo-complexes [Mo(η3-C3H5)(CO)(η2-pyS)(η2-diphos)] (diphos = dppm, 4a−4d; dppe, 5a−5d), are accessible by the reactions of 1 with dppm and dppe in refluxing acetonitrile. Homonuclear shift-correlated 2-D 31P{1H}−31P{1H} NMR experiments of the mixtures 4a−4d have been employed to elucidate the four stereoisomers. The reaction of 4 and pySK or [Mo(CO)3(η1-SC5H4NH)(η2-dppm)] (6) and O2 affords allyl-displaced seven-coordinate bis(pyridine-2-thionate) complex [Mo(CO)(η2-pyS)2(η2-dppm)] (7). All of the complexes are identified by spectroscopic methods, and complexes 1, 5d, 6, and 7 are determined by single-crystal X-ray diffraction. Complexes 1 and 5d crystallize in the orthorhombic space groups Pbcn and Pbca with Z = 4 and 8, respectively, whereas 6 belongs to the monoclinic space group C2/c with Z = 8 and 7 belongs to the triclinic space group P1̄ with Z = 2. The cell dimensions are as follows: for 1, a = 8.3128(1) Å, b = 16.1704(2) Å, c = 16.6140(2) Å; for 5d, a = 17.8309(10) Å, b = 17.3324(10) Å, c = 20.3716(11) Å; for 6, a = 18.618(4) Å, b = 16.062(2) Å, c = 27.456(6) Å, β = 96.31(3)°; for 7, a = 9.1660(2) Å, b = 12.0854(3) Å, c = 15.9478(4) Å, α = 78.4811(10)°, β = 80.3894(10)°, γ = 68.7089(11)°.
