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Both products were fully characterised (\u03bd<jats:sub>CO<\/jats:sub> IR; <jats:sup>1<\/jats:sup>H, <jats:sup>31<\/jats:sup>P, <jats:sup>13<\/jats:sup>C\u2005NMR spectroscopies) at low temperature; they lose H<jats:sub>2<\/jats:sub> upon warming to 230\u2005K at approximately the same rate (ca. 10<jats:sup>\u22123<\/jats:sup>\u2005s<jats:sup>\u22121<\/jats:sup>), with no detection of the non\u2010classical form in CD<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub>, to generate [Mo(CO)(Cp*)(FBF<jats:sub>3<\/jats:sub>)(PMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] (<jats:bold>4<\/jats:bold>). The latter also slowly decomposes at ambient temperature. One of the decomposition products was crystallised and identified by X\u2010ray crystallography as [Mo(CO)(Cp*)(FH\u22c5\u22c5\u22c5FBF<jats:sub>3<\/jats:sub>)(PMe<jats:sub>3<\/jats:sub>)<jats:sub>2<\/jats:sub>] (<jats:bold>5<\/jats:bold>), which features a neutral HF ligand coordinated to the transition metal through the F atom and to the BF<jats:sub>4<\/jats:sub><jats:sup>\u2212<\/jats:sup> anion through a hydrogen bond. The reason for the switch in relative stability between <jats:bold>2<\/jats:bold> and <jats:bold>3<\/jats:bold> was probed by DFT calculations based on the B3LYP and M05\u20102X functionals, with inclusion of anion and solvent effects by the conductor\u2010like polarisable continuum model and by explicit consideration of the solvent molecules. Calculations at the MP4(SDQ) and CCSD(T) levels were also carried out for calibration. The calculations reveal the key role of non\u2010covalent anion\u2013solvent interactions, which modulate the anion\u2013cation interaction ultimately altering the energetic balance between the two isomeric forms.<\/jats:p>","DOI":"10.1002\/chem.200901613","type":"journal-article","created":{"date-parts":[[2009,11,5]],"date-time":"2009-11-05T02:08:59Z","timestamp":1257386939000},"page":"189-201","source":"Crossref","is-referenced-by-count":29,"title":["Solvent\u2010Dependent Dihydrogen\/Dihydride Stability for [Mo(CO)(Cp*)H<sub>2<\/sub>(PMe<sub>3<\/sub>)<sub>2<\/sub>]<sup>+<\/sup>[BF<sub>4<\/sub>]<sup>\u2212<\/sup> Determined by Multiple Solvent\u22c5\u22c5\u22c5Anion\u22c5\u22c5\u22c5Cation Non\u2010Covalent Interactions"],"prefix":"10.1002","volume":"16","author":[{"given":"Pavel\u2005A.","family":"Dub","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Natalia\u2005V.","family":"Belkova","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Oleg\u2005A.","family":"Filippov","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Jean\u2010Claude","family":"Daran","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Lina\u2005M.","family":"Epstein","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Agust\u00ed","family":"Lled\u00f3s","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Elena\u2005S.","family":"Shubina","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Rinaldo","family":"Poli","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2009,12,23]]},"reference":[{"key":"e_1_2_7_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00314a049"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1007\/b113929"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr970322u"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2007.06.007"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2006.12.001"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr050197j"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar00147a005"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(92)80067-2"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00040a001"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0358450"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200400700"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic061428n"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2006.07.106"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/om8000235"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1039\/b608404b"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic981320a"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200305376"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200500695"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja029712a"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.molstruc.2007.03.040"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.200700021"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(01)01218-9"},{"key":"e_1_2_7_23_2","unstructured":"NMR spectroscopic properties of [MoCl(CO)(Cp*)(PMe3)2]:1H\u2005NMR (500\u2005MHz CD2Cl2):\u03b4=1.81 (s 15\u2009H Cp*) 1.41\u2005ppm (d 18\u2009H 2J(H P)=8\u2005Hz);31P{1H}\u2005NMR (500\u2005MHz CD2Cl2):\u03b4=17.9\u2005ppm (s)."},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00011a019"},{"key":"e_1_2_7_25_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00229a015"},{"key":"e_1_2_7_26_2","first-page":"1371","volume":"77","author":"Epstein L. 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