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We have investigated the depolymerization process of paraformaldehyde at different temperatures for the application as C1 surrogate in \u201cCO\u2010free\u201d carbonylation reactions using in situ Raman spectroscopy. Rather surprisingly, it was found that small amounts of commonly applied carbonylation catalysts slow down the depolymerization process significantly. By applying <jats:sup>1<\/jats:sup>H, <jats:sup>17<\/jats:sup>O, and <jats:sup>31<\/jats:sup>P\u2005NMR spectroscopy coupled with DFT calculations the inhibition process could be assigned to an electron\u2010withdrawing coordination behavior of the Pd complex at the chain end of the paraformaldehyde chain. This inhibition process can be controlled by the utilized phosphine ligand.<\/jats:p>","DOI":"10.1002\/chem.202000962","type":"journal-article","created":{"date-parts":[[2020,3,2]],"date-time":"2020-03-02T05:37:57Z","timestamp":1583127477000},"page":"5297-5302","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Controlling the Depolymerization of Paraformaldehyde with Pd\u2013Phosphine Complexes"],"prefix":"10.1002","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5419-4451","authenticated-orcid":false,"given":"Robert","family":"Geitner","sequence":"first","affiliation":[{"name":"Inorganic Chemistry and Catalysis Group Debye Institute for Nanomaterials Science Utrecht University  Universiteitsweg 99 3584 CG Utrecht The Netherlands"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5245-1426","authenticated-orcid":false,"given":"Bert M.","family":"Weckhuysen","sequence":"additional","affiliation":[{"name":"Inorganic Chemistry and Catalysis Group Debye Institute for Nanomaterials Science Utrecht University  Universiteitsweg 99 3584 CG Utrecht The Netherlands"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2020,4]]},"reference":[{"key":"e_1_2_7_1_1","first-page":"94","volume-title":"Ullmann's Encyclopedia of Industrial Chemistry","author":"Bertleff W.","year":"2000"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1007\/b105253"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/9783527651733.ch3"},{"key":"e_1_2_7_4_1","unstructured":"H.-J.Blankertz A. 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