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An analogous reaction of [MoBr(\u03b7<jats:sup>3<\/jats:sup>\u2010allyl)(CO)<jats:sub>2<\/jats:sub>(NCMe)<jats:sub>2<\/jats:sub>] yields [Mo(\u03b7<jats:sup>3<\/jats:sup>\u2010allyl)(CO)<jats:sub>2<\/jats:sub>([9]aneS<jats:sub>3<\/jats:sub>)][BAr\u2032<jats:sub>4<\/jats:sub>] (<jats:bold>2\u22c5BAr\u2032<jats:sub>4<\/jats:sub><\/jats:bold>). The new compounds <jats:bold>1\u22c5BAr\u2032<jats:sub>4<\/jats:sub><\/jats:bold> and <jats:bold>2\u22c5BAr\u2032<jats:sub>4<\/jats:sub><\/jats:bold> were characterized by IR and NMR spectroscopic analysis and X\u2010ray diffraction studies. Both compounds feature the cyclic thioether [9]aneS<jats:sub>3<\/jats:sub> coordinated as a tridentate ligand to the molybdenum center. The allyl ligand in <jats:bold>2\u22c5BAr\u2032<jats:sub>4<\/jats:sub><\/jats:bold> is aligned with the middle of the OC\u2010Mo\u2010CO angle, which is acute. Both of these features are typical of most pseudo\u2010octahedral allyl dicarbonyl molybdenum complexes. In contrast, the allyl group is rotated in <jats:bold>1\u22c5BAr\u2032<jats:sub>4<\/jats:sub><\/jats:bold>, which is attributed to steric hindrance between the methyl substituent and the ligated thioether, and the OC\u2010Mo\u2010CO angle is obtuse. Compound <jats:bold>1\u22c5BAr\u2032<jats:sub>4<\/jats:sub><\/jats:bold> undergoes rapid substitution of [9]aneS<jats:sub>3<\/jats:sub> by either chloride and fluoride ions in dichloromethane, and the products include the known species [{Mo(\u03b7<jats:sup>3<\/jats:sup>\u2010methallyl)(CO)<jats:sub>2<\/jats:sub>}<jats:sub>2<\/jats:sub>(\u03bc\u2010Cl)<jats:sub>3<\/jats:sub>]<jats:sup>\u2212<\/jats:sup> and a structurally similar new anionic complex with two fluoro and one hydroxo bridging ligands, respectively. Stable supramolecular adducts were formed in the reactions of <jats:bold>1\u22c5BAr\u2032<jats:sub>4<\/jats:sub><\/jats:bold> and <jats:bold>2\u22c5BAr<jats:sub>4<\/jats:sub><\/jats:bold> with bromide, iodide, hydrogensulfate, and methanesulfonate compounds. The binding constants of these adducts in dichloromethane were calculated from <jats:sup>1<\/jats:sup>H\u2005NMR spectroscopic titration data, and the solid\u2010state structures of the <jats:bold>1\u22c5Br<\/jats:bold>, <jats:bold>1\u22c5HSO<jats:sub>4<\/jats:sub><\/jats:bold>, <jats:bold>1\u22c5I<\/jats:bold>, and <jats:bold>2\u22c5I<\/jats:bold> adducts were determined by X\u2010ray diffraction studies. The surprising slightly higher stability of the iodide adduct relative to that of bromide was investigated theoretically, with the results pointing to an effect of the differential solvation of the halide ions.<\/jats:p>","DOI":"10.1002\/chem.201201327","type":"journal-article","created":{"date-parts":[[2012,10,23]],"date-time":"2012-10-23T11:23:30Z","timestamp":1350991410000},"page":"16186-16195","source":"Crossref","is-referenced-by-count":5,"title":["Interaction between Anions and Molybdenum Allyl Dicarbonyl Complexes of 1,4,7\u2010Trithiacyclononane"],"prefix":"10.1002","volume":"18","author":[{"given":"Dolores","family":"Morales","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Marcos","family":"Puerto","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ignacio","family":"del\u2005R\u00edo","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Julio","family":"P\u00e9rez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ram\u00f3n","family":"L\u00f3pez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2012,10,23]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010702)113:13<2446::AID-ANGE2446>3.0.CO;2-2"},{"key":"e_1_2_6_1_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010702)40:13<2382::AID-ANIE2382>3.0.CO;2-G"},{"key":"e_1_2_6_2_2","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/9783527639502"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1039\/b822552b"},{"key":"e_1_2_6_5_2","volume-title":"Anion Coordination Chemistry","author":"Sessler J. 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