Syntheses, Reactivity, and Crystal Structures of Molybdenum\nComplexes with Pyridine-2-thionate (pyS)-Containing Ligands: Crystal\nStructures 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>,\n<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)],\n[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)]
Kuang-Hway Yih (2095738)Gene-Hsiang Lee (1470748)Yu Wang (12152)
Abstract
The doubly bridged pyridine-2-thionate (pyS) dimolybdenum complex [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> (<b>1</b>) is\naccessible by the reaction of [Mo(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(CO)<sub>2</sub>(CH<sub>3</sub>CN)<sub>2</sub>Br] with pySK in methanol at room temperature. Complex\n<b>1</b> reacts with piperidine in acetonitrile to give the complex [Mo(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(CO)<sub>2</sub>(η<sup>2</sup>-pyS)(C<sub>5</sub>H<sub>10</sub>NH)] (<b>2</b>). Treatment of\n<b>1</b> with 1,10-phenanthroline (phen) results in the formation of complex [Mo(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(CO)<sub>2</sub>(η<sup>1</sup>-pyS)(phen)] (<b>3</b>), in\nwhich the pyS ligand is coordinated to Mo through the sulfur atom. Four conformational isomers, <i>endo</i>,<i>exo</i>-complexes\n[Mo(η<sup>3</sup>-C<sub>3</sub>H<sub>5</sub>)(CO)(η<sup>2</sup>-pyS)(η<sup>2</sup>-diphos)] (diphos = dppm, <b>4a</b><b>−</b><b>4d</b>; dppe, <b>5a</b><b>−</b><b>5d</b>), are accessible by the reactions of\n<b>1</b> with dppm and dppe in refluxing acetonitrile. Homonuclear shift-correlated 2-D <sup>31</sup>P{<sup>1</sup>H}−<sup>31</sup>P{<sup>1</sup>H} NMR experiments\nof the mixtures <b>4a</b><b>−</b><b>4d</b> have been employed to elucidate the four stereoisomers. The reaction of <b>4</b> and pySK or\n[Mo(CO)<sub>3</sub>(η<sup>1</sup>-SC<sub>5</sub>H<sub>4</sub>NH)(η<sup>2</sup>-dppm)] (<b>6</b>) and O<sub>2</sub> affords allyl-displaced seven-coordinate bis(pyridine-2-thionate) complex\n[Mo(CO)(η<sup>2</sup>-pyS)<sub>2</sub>(η<sup>2</sup>-dppm)] (<b>7</b>). All of the complexes are identified by spectroscopic methods, and complexes <b>1</b>,\n<b>5d</b>, <b>6</b>, and <b>7</b> are determined by single-crystal X-ray diffraction. Complexes <b>1</b> and <b>5d</b> crystallize in the orthorhombic\nspace groups <i>Pbcn</i> and <i>Pbca</i> with <i>Z</i> = 4 and 8, respectively, whereas <b>6</b> belongs to the monoclinic space group\n<i>C</i>2/<i>c</i> with <i>Z</i> = 8 and <b>7</b> belongs to the triclinic space group <i>P</i>1̄ with <i>Z</i> = 2. The cell dimensions are as follows: \nfor <b>1</b>, <i>a</i> = 8.3128(1) Å, <i>b</i> = 16.1704(2) Å, <i>c</i> = 16.6140(2) Å; for <b>5d</b>, <i>a</i> = 17.8309(10) Å, <i>b</i> = 17.3324(10) Å, <i>c</i>\n= 20.3716(11) Å; for <b>6</b>, <i>a</i> = 18.618(4) Å, <i>b</i> = 16.062(2) Å, <i>c</i> = 27.456(6) Å, β = 96.31(3)°; for <b>7</b>, <i>a</i> = 9.1660(2)\nÅ, <i>b</i> = 12.0854(3) Å,<i> c </i>= 15.9478(4) Å, α = 78.4811(10)°, β = 80.3894(10)°, γ = 68.7089(11)°.
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