{"doi":"10.1177/1469066718809881","title":"Isotope labeling and infrared multiple-photon photodissociation investigation of product ions generated by dissociation of [ZnNO\n                    <sub>3</sub>\n                    (CH\n                    <sub>3</sub>\n                    OH)\n                    <sub>2</sub>\n                    ]\n                    <sup>+</sup>\n                    : Conversion of methanol to formaldehyde","abstract":"<jats:p>\n                    Electrospray ionization was used to generate species such as [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)\n                    <jats:sub>2</jats:sub>\n                    ]\n                    <jats:sup>+</jats:sup>\n                    from Zn(NO\n                    <jats:sub>3</jats:sub>\n                    )\n                    <jats:sub>2</jats:sub>\n                    •XH\n                    <jats:sub>2</jats:sub>\n                    O dissolved in a mixture of CH\n                    <jats:sub>3</jats:sub>\n                    OH and H\n                    <jats:sub>2</jats:sub>\n                    O. Collision-induced dissociation of [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)\n                    <jats:sub>2</jats:sub>\n                    ]\n                    <jats:sup>+</jats:sup>\n                    causes elimination of CH\n                    <jats:sub>3</jats:sub>\n                    OH to form [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    . Subsequent collision-induced dissociation of [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    causes elimination of 47 mass units (u), consistent with ejection of HNO\n                    <jats:sub>2</jats:sub>\n                    . The neutral loss shifts to 48 u for collision-induced dissociation of [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CD\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    , demonstrating the ejection of HNO\n                    <jats:sub>2</jats:sub>\n                    involves intra-complex transfer of H from the methyl group methanol ligand. Subsequent collision-induced dissociation causes the elimination of 30 u (32 u for the complex with CD\n                    <jats:sub>3</jats:sub>\n                    OH), suggesting the elimination of formaldehyde (CH\n                    <jats:sub>2</jats:sub>\n                     = O). The product ion is [ZnOH]\n                    <jats:sup>+</jats:sup>\n                    . Collision-induced dissociation of a precursor complex created using CH\n                    <jats:sub>3</jats:sub>\n                    -\n                    <jats:sup>18</jats:sup>\n                    OH shows the isotope label is retained in CH\n                    <jats:sub>2</jats:sub>\n                     = O. Density functional theory calculations suggested that the “rearranged” product, ZnOH with bound HNO\n                    <jats:sub>2</jats:sub>\n                    and formaldehyde is significantly lower in energy than ZnNO\n                    <jats:sub>3</jats:sub>\n                    with bound methanol. We therefore used infrared multiple-photon photodissociation spectroscopy to determine the structures of both [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)\n                    <jats:sub>2</jats:sub>\n                    ]\n                    <jats:sup>+</jats:sup>\n                    and [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    . The infrared spectra clearly show that both ions contain intact nitrate and methanol ligands, which suggests that rearrangement occurs during collision-induced dissociation of [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    . Based on the density functional theory calculations, we propose that transfer of H, from the methyl group of the CH\n                    <jats:sub>3</jats:sub>\n                    OH ligand to nitrate, occurs in concert with the formation of a Zn–C bond. After dissociation to release HNO\n                    <jats:sub>2</jats:sub>\n                    , the product rearranges with the insertion of the remaining O atom into the Zn–C bond. Subsequent C–O bond cleavage, with H transfer, produces an ion–molecule complex composed of [ZnOH]\n                    <jats:sup>+</jats:sup>\n                    and O = CH\n                    <jats:sub>2</jats:sub>\n                    .\n                  </jats:p>","journal":"European Journal of Mass Spectrometry","year":2019,"id":607131,"datarank":0.0,"base_score":0.0,"endowment":0.0,"self_citation_contribution":0.0,"citation_network_contribution":0.0,"self_endowment_contribution":0.0,"citer_contribution":0.0,"corpus_percentile":null,"corpus_rank":null,"citation_count":0,"citer_count":0,"citers_with_citation_signal":0,"citers_with_endowment":0,"datacite_reuse_total":0,"is_dataset":false,"is_dataset_confidence":null,"is_data_producer":false,"deposit_databanks":null,"is_oa":false,"file_count":0,"downloads":0,"has_version_chain":false,"published_date":null,"fair_score":null,"fair_percentile":null,"algorithm_id":"datarank_citation_only_1hop_v6","ranking_scope":"data_only","authors":[{"id":777195,"name":"Theodore A. Corcovilos","orcid":"0000-0001-5716-1188","position":1,"is_corresponding":false},{"id":1558827,"name":"John K Gibson","orcid":null,"position":2,"is_corresponding":false},{"id":780529,"name":"Jonathan Martens","orcid":"0000-0001-9537-4117","position":3,"is_corresponding":false},{"id":780530,"name":"Giel Berden","orcid":"0000-0003-1500-922X","position":4,"is_corresponding":false},{"id":780531,"name":"Jos Oomens","orcid":"0000-0002-2717-1278","position":5,"is_corresponding":false},{"id":1558828,"name":"Michael J Van Stipdonk","orcid":null,"position":6,"is_corresponding":false},{"id":513491,"name":"Evan Perez","orcid":"0000-0002-0837-4723","position":0,"is_corresponding":false}],"reference_count":0,"raw_metadata":{"has_enrichment":true,"resolved":true,"title":"Isotope labeling and infrared multiple-photon photodissociation investigation of product ions generated by dissociation of [ZnNO\n                    <sub>3</sub>\n                    (CH\n                    <sub>3</sub>\n                    OH)\n                    <sub>2</sub>\n                    ]\n                    <sup>+</sup>\n                    : Conversion of methanol to formaldehyde","abstract":"<jats:p>\n                    Electrospray ionization was used to generate species such as [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)\n                    <jats:sub>2</jats:sub>\n                    ]\n                    <jats:sup>+</jats:sup>\n                    from Zn(NO\n                    <jats:sub>3</jats:sub>\n                    )\n                    <jats:sub>2</jats:sub>\n                    •XH\n                    <jats:sub>2</jats:sub>\n                    O dissolved in a mixture of CH\n                    <jats:sub>3</jats:sub>\n                    OH and H\n                    <jats:sub>2</jats:sub>\n                    O. Collision-induced dissociation of [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)\n                    <jats:sub>2</jats:sub>\n                    ]\n                    <jats:sup>+</jats:sup>\n                    causes elimination of CH\n                    <jats:sub>3</jats:sub>\n                    OH to form [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    . Subsequent collision-induced dissociation of [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    causes elimination of 47 mass units (u), consistent with ejection of HNO\n                    <jats:sub>2</jats:sub>\n                    . The neutral loss shifts to 48 u for collision-induced dissociation of [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CD\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    , demonstrating the ejection of HNO\n                    <jats:sub>2</jats:sub>\n                    involves intra-complex transfer of H from the methyl group methanol ligand. Subsequent collision-induced dissociation causes the elimination of 30 u (32 u for the complex with CD\n                    <jats:sub>3</jats:sub>\n                    OH), suggesting the elimination of formaldehyde (CH\n                    <jats:sub>2</jats:sub>\n                     = O). The product ion is [ZnOH]\n                    <jats:sup>+</jats:sup>\n                    . Collision-induced dissociation of a precursor complex created using CH\n                    <jats:sub>3</jats:sub>\n                    -\n                    <jats:sup>18</jats:sup>\n                    OH shows the isotope label is retained in CH\n                    <jats:sub>2</jats:sub>\n                     = O. Density functional theory calculations suggested that the “rearranged” product, ZnOH with bound HNO\n                    <jats:sub>2</jats:sub>\n                    and formaldehyde is significantly lower in energy than ZnNO\n                    <jats:sub>3</jats:sub>\n                    with bound methanol. We therefore used infrared multiple-photon photodissociation spectroscopy to determine the structures of both [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)\n                    <jats:sub>2</jats:sub>\n                    ]\n                    <jats:sup>+</jats:sup>\n                    and [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    . The infrared spectra clearly show that both ions contain intact nitrate and methanol ligands, which suggests that rearrangement occurs during collision-induced dissociation of [ZnNO\n                    <jats:sub>3</jats:sub>\n                    (CH\n                    <jats:sub>3</jats:sub>\n                    OH)]\n                    <jats:sup>+</jats:sup>\n                    . Based on the density functional theory calculations, we propose that transfer of H, from the methyl group of the CH\n                    <jats:sub>3</jats:sub>\n                    OH ligand to nitrate, occurs in concert with the formation of a Zn–C bond. After dissociation to release HNO\n                    <jats:sub>2</jats:sub>\n                    , the product rearranges with the insertion of the remaining O atom into the Zn–C bond. Subsequent C–O bond cleavage, with H transfer, produces an ion–molecule complex composed of [ZnOH]\n                    <jats:sup>+</jats:sup>\n                    and O = CH\n                    <jats:sub>2</jats:sub>\n                    .\n                  </jats:p>","is_dataset_classified":null,"base_score":0.0,"endowment":0.0,"datacite_reuse_total":0,"file_count":0,"downloads":0,"views":0,"has_version_chain":false,"is_dataset":false,"is_oa":false,"pmid":"30773924","pmcid":null,"openalex_id":"https://openalex.org/W2917881520","authors":[],"funders":[{"funder_name":"National Science Foundation","grant_id":"CHE-0963450","title":null},{"funder_name":"Netherlands Organization for Scientific Research","grant_id":"vici-grant 724.011.002","title":null},{"funder_name":"U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Elements Chemistry","grant_id":"DE-AC02-05CH11231","title":null},{"funder_name":"Robert Dean Loughney Faculty Development Fund","grant_id":"","title":null}],"total_grants":4,"fwci":0.0,"citation_percentile":0.01465947,"influential_citations":0,"citation_trend":[],"oa_status":"bronze","license":"http://www.sagepub.com/licence-information-for-chorus","oa_locations":[{"url":"https://journals.sagepub.com/doi/pdf/10.1177/1469066718809881","host_type":"journal"},{"url":"https://journals.sagepub.com/doi/pdf/10.1177/1469066718809881","host_type":"publisher"},{"url":"https://journals.sagepub.com/doi/full-xml/10.1177/1469066718809881","host_type":"publisher"},{"url":"https://doi.org/10.1177/1469066718809881","host_type":"journal"},{"url":"https://pubmed.ncbi.nlm.nih.gov/30773924","host_type":"repository"},{"url":"https://hdl.handle.net/11245.1/b4469eb4-c372-4184-8a8d-4141e947a562","host_type":"repository"},{"url":"https://handle.uba.uva.nl/personal/pure/en/publications/isotope-labeling-and-infrared-multiplephoton-photodissociation-investigation-of-product-ions-generated-by-dissociation-of-znno3ch3oh2-conversion-of-methanol-to-formaldehyde(b4469eb4-c372-4184-8a8d-4141e947a562).html","host_type":"repository"},{"url":"http://hdl.handle.net/2066/201519","host_type":"repository"},{"url":"https://dare.uva.nl/personal/pure/en/publications/isotope-labeling-and-infrared-multiplephoton-photodissociation-investigation-of-product-ions-generated-by-dissociation-of-znno3ch3oh2-conversion-of-methanol-to-formaldehyde(b4469eb4-c372-4184-8a8d-4141e947a562).html","host_type":"repository"}],"fields_of_study":["Mass Spectrometry Techniques and Applications","Spectroscopy and Quantum Chemical Studies","Isotope Analysis in Ecology"],"mesh_terms":[],"keywords":["Chemistry","Dissociation (chemistry)","Photodissociation","Collision-induced dissociation","Formaldehyde","Methanol","Photochemistry","Density functional theory","Mass spectrometry","Ion","Analytical Chemistry (journal)","Tandem mass spectrometry","Computational chemistry","Physical chemistry","Organic chemistry","Chromatography","Ion Spectroscopy","Ion Structure","Metal-mediated Reactions","Infrared Multiple-photon Photodissociation"],"sdg_mappings":[],"linked_datasets":[],"clinical_trials":[],"software_tools":[],"database_accessions":[],"source":"live","citation_network_status":"fetched"},"created_at":"2026-07-30T05:50:59.132363Z","pmid":null,"pmcid":null,"fwci":null,"citation_percentile":null,"influential_citations":0,"oa_status":null,"license":null,"views":0,"total_file_size_bytes":0,"version_count":0,"fair_f":null,"fair_a":null,"fair_i":null,"fair_r":null,"fair_zscore":null,"fair_rationale":null,"fair_model":null,"fair_agent_version":null,"fair_fulltext_source":null,"fair_has_llm":null,"fair_computed_at":null,"clinical_trials":[],"software_tools":[],"db_accessions":[],"linked_datasets":[],"topics":[]}