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The aromatic pyridine ring and the phosphine PR<jats:sub>2<\/jats:sub> moieties are connected through NH, <jats:italic>N<\/jats:italic>\u2010alkyl, or <jats:italic>N<\/jats:italic>\u2010aryl linkers. For bulky PNP ligands, with the exception of the ligands with P<jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub> units, these complexes are obtained upon the treatment of [Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP)Cl<jats:sub>2<\/jats:sub>] with CO. With small PNP ligands, such complexes are not accessible directly owing to the formation of [Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP)(\u03ba<jats:sup>2<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010PNP)Cl]Cl. These complexes liberate the \u03ba<jats:sup>2<\/jats:sup>\u2010<jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010bound PNP ligand in the presence of CO to yield [Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP)(CO)Cl<jats:sub>2<\/jats:sub>] in yields of less than 50\u2009%. High yields are achieved by reacting FeCl<jats:sub>2<\/jats:sub> with PNP ligands under a CO atmosphere. For structural and reactivity comparisons, [Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP\u2010Ph)(\u03ba<jats:sup>2<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>\u2010PN\u2010Ph)Cl]<jats:sup>+<\/jats:sup> was prepared, and this complex does not react with CO. In contrast to the reactions in solution, in the solid state, complexes [Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP)Cl<jats:sub>2<\/jats:sub>] with NH linkers are also converted quantitatively into <jats:italic>trans<\/jats:italic>\u2010 or <jats:italic>cis<\/jats:italic>\u2010[Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP)(CO)(Cl)<jats:sub>2<\/jats:sub>] upon treatment with CO, as indicated by a color change and by IR spectroscopy monitoring. Those with <jats:italic>N<\/jats:italic>\u2010alkyl and <jats:italic>N<\/jats:italic>\u2010aryl linkers did not react with CO. To rationalize why most [Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP)Cl<jats:sub>2<\/jats:sub>] complexes react readily with CO but those with <jats:italic>t<\/jats:italic>Bu substituents do not, the additions of CO to [Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP\u2010<jats:italic>i<\/jats:italic>Pr)Cl<jats:sub>2<\/jats:sub>] and [Fe(\u03ba<jats:sup>3<\/jats:sup><jats:italic>P<\/jats:italic>,<jats:italic>N<\/jats:italic>,<jats:italic>P<\/jats:italic>\u2010PNP\u2010<jats:italic>t<\/jats:italic>Bu)Cl<jats:sub>2<\/jats:sub>] were investigated by DFT calculations.<\/jats:p>","DOI":"10.1002\/ejic.201500646","type":"journal-article","created":{"date-parts":[[2015,9,30]],"date-time":"2015-09-30T07:49:01Z","timestamp":1443599341000},"page":"5053-5065","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":23,"title":["Fe<sup>II<\/sup> Carbonyl Complexes Featuring Small to Bulky PNP Pincer Ligands \u2013 Facile Substitution of \u03ba<sup>2<\/sup><i>P<\/i>,<i>N<\/i>\u2010Bound PNP Ligands by Carbon Monoxide"],"prefix":"10.1002","volume":"2015","author":[{"given":"Mathias","family":"Glatz","sequence":"first","affiliation":[]},{"given":"Christian","family":"Holzhacker","sequence":"additional","affiliation":[]},{"given":"Bernhard","family":"Bichler","sequence":"additional","affiliation":[]},{"given":"Matthias","family":"Mastalir","sequence":"additional","affiliation":[]},{"given":"Berthold","family":"St\u00f6ger","sequence":"additional","affiliation":[]},{"given":"Kurt","family":"Mereiter","sequence":"additional","affiliation":[]},{"given":"Matthias","family":"Weil","sequence":"additional","affiliation":[]},{"given":"Luis F.","family":"Veiros","sequence":"additional","affiliation":[]},{"given":"Nadia C.","family":"M\u00f6sch\u2010Zanetti","sequence":"additional","affiliation":[]},{"given":"Karl","family":"Kirchner","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2015,9,30]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"For reviews on pincer complexes see:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20011015)40:20<3750::AID-ANIE3750>3.0.CO;2-6"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr960118r"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(02)01511-9"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1080\/02603594.2011.618855"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201100880"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/B978-044453138-4\/50010-6"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar700129q"},{"key":"e_1_2_6_9_2","unstructured":"\u00a0"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/j19710002184"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0020-1693(00)89120-3"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3749(200213)628:13<2839::AID-ZAAC2839>3.0.CO;2-9"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2005.11.039"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ic0608647"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/om800425p"},{"key":"e_1_2_6_16_2","unstructured":"\u00a0"},{"key":"e_1_2_6_17_2","first-page":"60","author":"Wong A.","year":"2014","journal-title":"J. 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