{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T04:32:21Z","timestamp":1792643541311,"version":"4.5.0"},"reference-count":39,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2023,4,21]],"date-time":"2023-04-21T00:00:00Z","timestamp":1682035200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100006770","name":"ACS PRF","doi-asserted-by":"publisher","award":["58937-ND3"],"award-info":[{"award-number":["58937-ND3"]}],"id":[{"id":"10.13039\/100006770","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>In this study, we report the synthesis, characterization, and reactions of Cu(I) complexes of the general form Cu(L)(LigH2) (LigH2 = xanthene-based heterodinucleating ligand (E)-3-(((5-(bis(pyridin-2-ylmethyl)amino)-2,7-di-tert-butyl-9,9-dimethyl-9H-xanthen-4-yl)imino)methyl)benzene-1,2-diol); L = PMe3, PPh3, CN(2,6-Me2C6H3)). New complexes [Cu(PMe3)(LigH2)] and [CuCN(2,6-Me2C6H3)(LigH2)] were synthesized by treating [Cu(LigH2)](PF6) with trimethylphosphine and 2,6-dimethylphenyl isocyanide, respectively. These complexes were characterized by multinuclear NMR spectroscopy, IR spectroscopy, high-resolution mass spectrometry (HRMS), and X-ray crystallography. In contrast, attempted reactions of [Cu(LigH2)](PF6) with cyanide or styrene failed to produce isolable crystalline products. Next, the reactivity of these and previously synthesized Cu(I) phosphine and isocyanide complexes with molybdate was interrogated. IR (for isocyanide) and 31P NMR (for PPh3\/PMe3) spectroscopy demonstrates the lack of oxidation reactivity. We also describe herein the first example of a structurally characterized multinuclear complex combining both Mo(VI) and Cu(I) metal ions within the same system. The heterobimetallic tetranuclear complex [Cu2Mo2O4(\u03bc2-O)(Lig)2]\u00b7HOSiPh3 was obtained by the reaction of the silylated Mo(VI) precursor (Et4N)(MoO3(OSiPh3)) with LigH2, followed by the addition of [Cu(NCMe)4](PF6). This complex was characterized by NMR spectroscopy, high-resolution mass spectrometry, and X-ray crystallography.<\/jats:p>","DOI":"10.3390\/molecules28083644","type":"journal-article","created":{"date-parts":[[2023,4,24]],"date-time":"2023-04-24T02:31:05Z","timestamp":1682303465000},"page":"3644","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Studies Relevant to the Functional Model of Mo-Cu CODH: In Situ Reactions of Cu(I)-L Complexes with Mo(VI) and Synthesis of Stable Structurally Characterized Heterotetranuclear MoVI2CuI2 Complex"],"prefix":"10.3390","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5144-9949","authenticated-orcid":false,"given":"Umesh I.","family":"Kaluarachchige Don","sequence":"first","affiliation":[{"name":"Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, MI 48202, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ahmad S.","family":"Almaat","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, MI 48202, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Cassandra L.","family":"Ward","sequence":"additional","affiliation":[{"name":"Lumigen Instrument Center, Wayne State University, 5101 Cass Avenue, Detroit, MI 48202, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3578-7985","authenticated-orcid":false,"given":"Stanislav","family":"Groysman","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Wayne State University, 5101 Cass Avenue, Detroit, MI 48202, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2023,4,21]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"243","DOI":"10.1007\/s00775-014-1188-4","article-title":"The aerobic CO dehydrogenase from Oligotropha carboxidovorans","volume":"20","author":"Hille","year":"2015","journal-title":"J. Biol. Inorg. Chem."},{"key":"ref_2","first-page":"61","article-title":"Microbial growth on carbon monoxide","volume":"3","author":"Frunzke","year":"1992","journal-title":"Biodegradation"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"101","DOI":"10.1007\/430_2019_31","article-title":"The Role of the Pyranopterin Dithiolene Component of Moco in Molybdoenzyme Catalysis","volume":"Volume 179","author":"Ribbe","year":"2019","journal-title":"Structure and Bonding: Metallocofactors that Activate Small Molecules"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"373","DOI":"10.1007\/s00775-014-1228-0","article-title":"Recent Developments in the Study of Molybdoenzyme Models","volume":"20","author":"Basu","year":"2015","journal-title":"J. Biol. Inorg. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"15971","DOI":"10.1073\/pnas.212640899","article-title":"Catalysis at a dinuclear [CuSMo(AO)OH] cluster in a CO dehydrogenase resolved at 1.1-\u00c5 resolution","volume":"99","author":"Dobbek","year":"2002","journal-title":"Proc. Natl. Acad. Sci USA"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"36052","DOI":"10.1074\/jbc.M113.522441","article-title":"The hydrogenase activity of the molybdenum\/copper-containing carbon monoxide dehydrogenase of Oligotropha carboxidovorans","volume":"288","author":"Wilcoxen","year":"2013","journal-title":"J. Biol. Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"222","DOI":"10.1021\/bi026514n","article-title":"A novel binuclear [CuSMo] cluster at the active site of carbon monoxide dehydrogenase: Characterization by X-ray absorption spectroscopy","volume":"42","author":"Gnida","year":"2003","journal-title":"Biochemistry"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"12571","DOI":"10.1074\/jbc.M109.076851","article-title":"Kinetic and spectroscopic studies of the molybdenum-copper CO dehydrogenase from Oligotropha carboxidovorans","volume":"285","author":"Zhang","year":"2010","journal-title":"J. Biol. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"17775","DOI":"10.1021\/ja406136f","article-title":"13C and 63,65Cu ENDOR studies of CO Dehydrogenase from Oligotropha carboxidovorans. Experimental Evidence in Support of a Copper\u2013Carbonyl Intermediate","volume":"135","author":"Shanmugam","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"888","DOI":"10.1002\/jcc.20230","article-title":"Quantum chemical modeling of CO oxidation by the active site of molybdenum CO dehydrogenase","volume":"26","author":"Siegbahn","year":"2005","journal-title":"J. Comput. Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"490","DOI":"10.1007\/s00775-005-0661-5","article-title":"The mechanism of Mo-\/Cu-dependent CO dehydrogenase","volume":"10","author":"Hofmann","year":"2005","journal-title":"J. Biol. Inorg. Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"1104","DOI":"10.1039\/C3CC47705C","article-title":"Orbital contributions to CO oxidation in Mo\u2013Cu carbon monoxide dehydrogenase","volume":"50","author":"Stein","year":"2014","journal-title":"Chem. Commun."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"491","DOI":"10.1007\/s00775-016-1359-6","article-title":"A realistic in silico model for structure\/function studies of molybdenum\u2013copper CO dehydrogenase","volume":"21","author":"Rokhsana","year":"2016","journal-title":"J. Biol. Inorg. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"18938","DOI":"10.1039\/C8CP00858B","article-title":"Revisiting the catalytic mechanism of Mo\u2013Cu carbon monoxide dehydrogenase using QM\/MM and DFT calculations","volume":"20","author":"Xu","year":"2018","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"630","DOI":"10.3389\/fchem.2018.00630","article-title":"The challenging in silico description of carbon monoxide oxidation as catalyzed by molybdenum-copper CO dehydrogenase","volume":"6","author":"Rovaletti","year":"2019","journal-title":"Front. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"201","DOI":"10.1016\/j.jcat.2019.02.032","article-title":"A thiocarbonate sink on the enzymatic energy landscape of aerobic CO oxidation? Answers from DFT and QM\/MM models of MoCu CO-dehydrogenases","volume":"372","author":"Rovaletti","year":"2019","journal-title":"J. Catal."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"7336","DOI":"10.1021\/acscatal.2c01408","article-title":"Unraveling the reaction mechanism of Mo\/Cu CO dehydrogenase using QM\/MM calculations","volume":"12","author":"Ritacca","year":"2022","journal-title":"ACS Catal."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"12135","DOI":"10.1039\/C4DT00729H","article-title":"Bioinorganic Modeling Chemistry of Carbon Monoxide Dehydrogenases: Description of Model Complexes, Current Status and Possible Future Scopes","volume":"43","author":"Majumdar","year":"2014","journal-title":"Dalton Trans."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2164","DOI":"10.1021\/ja056500f","article-title":"Paramagnetic active site models for the molybdenum\u2013copper carbon monoxide dehydrogenase","volume":"128","author":"Gourlay","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"876","DOI":"10.1039\/C7SC04239F","article-title":"Models for Aerobic Carbon Monoxide Dehydrogenase","volume":"9","author":"Gourlay","year":"2018","journal-title":"Chem. Sci."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"6034","DOI":"10.1021\/ic050294v","article-title":"Sulfido-Bridged Dinuclear Molybdenum\u2013Copper Complexes Related to the Active Site of CO Dehydrogenase: [(dithiolate)Mo(O)S2Cu(SAr)]2\u2212 (dithiolate = 1,2-S2C6H4, 1,2-S2C6H2-3,6-Cl2, 1,2-S2C2H4)","volume":"44","author":"Takuma","year":"2005","journal-title":"Inorg. Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1082","DOI":"10.1021\/ic902066m","article-title":"Reactions of monodithiolene tungsten(VI) sulfido complexes with copper(I) in relation to the structure of the active site of carbon monoxide dehydrogenase","volume":"49","author":"Groysman","year":"2010","journal-title":"Inorg. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"5503","DOI":"10.1039\/D0SC01045F","article-title":"A Bioinspired Molybdenum\u2013Copper Molecular Catalyst for CO2 Electroreduction","volume":"11","author":"Mouchfiq","year":"2020","journal-title":"Chem. Sci."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"12635","DOI":"10.1021\/jacs.0c03343","article-title":"A W\/Cu Synthetic Model for the Mo\/Cu Cofactor of Aerobic CODH indicates that Biochemical CO Oxidation Requires a Frustrated Lewis Acid\/Base Pair","volume":"142","author":"Ghosh","year":"2020","journal-title":"J. Am. Chem. Soc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"10017","DOI":"10.1039\/C8DT02323A","article-title":"Cooperative Bimetallic Reactivity of a Heterodinuclear Molybdenum-Copper Model of Mo-Cu CODH","volume":"47","author":"Hollingsworth","year":"2018","journal-title":"Dalton Trans."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"14655","DOI":"10.1021\/acs.inorgchem.1c01735","article-title":"Synthesis and Cu(I)\/Mo(VI) reactivity of a bifunctional heterodinucleating ligand on a xanthene platform","volume":"60","author":"Kurup","year":"2021","journal-title":"Inorg. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"11565","DOI":"10.1039\/C9DT02475A","article-title":"Mono- and Bimetallic Pentacoordinate Silicon Complexes of a Chelating Bis(catecholimine) Ligand","volume":"48","author":"Do","year":"2019","journal-title":"Dalton Trans."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"429","DOI":"10.1021\/ja9729239","article-title":"Syntheses and Structural Characterizations of the First 16-, 17-, and 18-Electron Homoleptic Isocyanide Complexes of Vanadium:\u2009 Hexakis(2,6-dimethyl- phenyl isocyanide)vanadium(I, 0, \u2013I)1","volume":"120","author":"Barybin","year":"1998","journal-title":"J. Am. Chem. Soc."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2309","DOI":"10.1021\/acs.organomet.6b00297","article-title":"A Well-Defined Isocyano Analogue of HCo(CO)4. 1: Synthesis, Decomposition, and Catalytic 1,1-Hydrogenation of Isocyanides","volume":"35","author":"Carpenter","year":"2016","journal-title":"Organometallics"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"45","DOI":"10.1002\/mrc.1270060112","article-title":"A C-NMR and IR study of isocyanides and some of their complexes","volume":"6","author":"Stephany","year":"1974","journal-title":"Org. Magn. Reason."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"11156","DOI":"10.1021\/ic701294y","article-title":"Silylation, Sulfidation, and Benzene-1,2-dithiolate Complexation Reactions of Oxo- and Oxosulfidomolybdates(VI) and -Tungstates(VI)","volume":"46","author":"Wang","year":"2007","journal-title":"Inorg. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"7512","DOI":"10.1021\/ja0724442","article-title":"Synthesis of Structural Analogues of the Oxidized Sites in the Xanthine Oxidoreductase Enzyme Family","volume":"129","author":"Wang","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"12794","DOI":"10.1021\/ja804000k","article-title":"A Biomimetic Approach to Oxidized Sites in the Xanthine Oxidoreductase Family: Synthesis and Stereochemistry of Tungsten(VI) Analogue Complexes","volume":"130","author":"Groysman","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"8609","DOI":"10.1021\/ic040097g","article-title":"Oxygen\/Sulfur Substitution Reactions of Tetraoxometalates Effected by Electrophilic Carbon and Silicon Reagents","volume":"43","author":"Partyka","year":"2004","journal-title":"Inorg. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"5865","DOI":"10.1002\/ejic.201402611","article-title":"Synthesis, Structures, and Reactivity of Copper(I) Complexes Supported by a Rigid Dinucleating Ligand","volume":"34","author":"Bheemaraju","year":"2014","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"5605","DOI":"10.1039\/C6DT04532D","article-title":"Divergent Reactivity of a New Dinuclear Xanthene-Bridged Bis(iminopyridine) di-Nickel Complex with Alkynes","volume":"46","author":"Hollingsworth","year":"2017","journal-title":"Dalton Trans."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053273314026370","article-title":"SHELXT\u2014Integrated Space-group and Crystal Structure Determination","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. Sect. A Found. Adv."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053229614024218","article-title":"Crystal Structure Refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. Sect. C Struct. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"339","DOI":"10.1107\/S0021889808042726","article-title":"OLEX2: A complete structure solution refinement and analysis program","volume":"42","author":"Dolomanov","year":"2009","journal-title":"J. Appl. Cryst."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/8\/3644\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T19:20:59Z","timestamp":1760124059000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/8\/3644"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,4,21]]},"references-count":39,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2023,4]]}},"alternative-id":["molecules28083644"],"URL":"https:\/\/doi.org\/10.3390\/molecules28083644","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,4,21]]}}}