{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,15]],"date-time":"2026-01-15T12:00:05Z","timestamp":1768478405629,"version":"3.49.0"},"reference-count":42,"publisher":"MDPI AG","issue":"13","license":[{"start":{"date-parts":[[2023,6,23]],"date-time":"2023-06-23T00:00:00Z","timestamp":1687478400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The objective of this study is to design and synthesize substituted \u03b76-chromium(0) tricarbonyl metal complexes carrying o-carborane units as potential boron neutron capture therapy (BNCT) agents. In this study, 1,2-diphenyl-o-carborane (1) units were used as starting materials to generate biologically active species. We investigated how the structural changes of 1 substituted with chromium(0) tricarbonyl affect the biological properties, and 1-(Phenyl-\u03b76-chromium(0) tricarbonyl)-2-phenyl-o-carborane (2) and 1,2-bis(phenyl-\u03b76-chromium(0) tricarbonyl)-o-carborane (3) species were produced in moderate yields. The molecular structures of compounds 1\u20133 were identified and established by infrared (IR); 1H, 11B, and 13C nuclear magnetic resonance (NMR) and X-ray crystallography analyses. Crystal structures of 1,2-diphenyl-o-carborane and the corresponding chromium complexes 1, 2, and 3 were obtained. In an in vitro study using B16 and CT26 cancer cells containing the triphenyl-o-carboranyl chromium(0) complexes Ph3C2BCr2 and Ph3C2BCr3, which we reported previously, compounds 2 and 3 accumulated at higher levels than compounds Ph3C2BCr2 and Ph3C2BCr3. However, the phenylated o-carboranyl chromium complexes have been found to be more cytotoxic than p-boronophenylalanine (BPA).<\/jats:p>","DOI":"10.3390\/molecules28134942","type":"journal-article","created":{"date-parts":[[2023,6,26]],"date-time":"2023-06-26T05:11:54Z","timestamp":1687756314000},"page":"4942","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["1,2-Diphenyl-o-carborane and Its Chromium Derivatives: Synthesis, Characterization, X-ray Structural Studies, and Biological Evaluations"],"prefix":"10.3390","volume":"28","author":[{"given":"Tae-Jin","family":"Ha","sequence":"first","affiliation":[{"name":"Department of Chemistry, College of Natural Sciences, Chosun University, 309 Pilmundaero, Gwangju 61452, Republic of Korea"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dong-Kyung","family":"Im","sequence":"additional","affiliation":[{"name":"Department of Chemistry, College of Natural Sciences, Chosun University, 309 Pilmundaero, Gwangju 61452, Republic of Korea"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Seung-Min","family":"Kim","sequence":"additional","affiliation":[{"name":"Department of Chemistry, College of Natural Sciences, Chosun University, 309 Pilmundaero, Gwangju 61452, Republic of Korea"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8297-6693","authenticated-orcid":false,"given":"Jong-Dae","family":"Lee","sequence":"additional","affiliation":[{"name":"Department of Chemistry, College of Natural Sciences, Chosun University, 309 Pilmundaero, Gwangju 61452, Republic of Korea"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,6,23]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"143","DOI":"10.1016\/j.canlet.2008.01.021","article-title":"Boron neutron capture therapy for glioblastoma","volume":"262","author":"Yamamoto","year":"2008","journal-title":"Cancer Lett."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"852","DOI":"10.1590\/S0004-27302007000500024","article-title":"Boron neutron capture therapy in cancer: Past, present and future","volume":"51","author":"Pisarev","year":"2007","journal-title":"Arq Bras Endocrinol Metab."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1646","DOI":"10.1135\/cccc20071646","article-title":"Boron units as pharmacophores\u2014New applications and opportunities of boron cluster chemistry","volume":"72","author":"Lesnikowski","year":"2007","journal-title":"Collect. Czech. Chem. Commun."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Tjarks, W., Tiwari, R., Byun, Y., Narayanasamy, S., and Barth, R.F. (2007). Carboranyl thymidine analogues for neutron capture therapy. Chem. Commun., 4978\u20134991.","DOI":"10.1039\/b707257k"},{"key":"ref_5","unstructured":"Bregadze, V.I., and Sivaev, I.B. (2011). Polyhedral Boron Compounds for BNCT in Boron Science: New Technologies and Applications, CRC Press. Chapter 9."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"4240","DOI":"10.1039\/b709843j","article-title":"The bioinorganic and medicinal chemistry of carboranes: From new drug discovery to molecular imaging and therapy","volume":"38","author":"Armstrong","year":"2007","journal-title":"Dalton Trans."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"5208","DOI":"10.1021\/cr050548u","article-title":"Chemistry of the Carba-closo-dodecaborate(\u2212) Anion, CB11H12\u2212","volume":"106","author":"Korbe","year":"2006","journal-title":"Chem. Rev."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"9398","DOI":"10.1039\/c3cc45313h","article-title":"A three-dimensional \u03c0-electron acceptor, tri-phenyl-o-carborane, bearing a rigid conformation with end-on phenyl units","volume":"49","author":"Jin","year":"2013","journal-title":"Chem. Commun."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"100","DOI":"10.1016\/j.jorganchem.2018.02.048","article-title":"B-phenylated o-carboranes and its chromium derivatives: Synthesis, electrochemical properties, and X-ray structural studies","volume":"865","author":"Kim","year":"2018","journal-title":"J. Organomet. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Abel, E.W., Stone, F.G.A., and Wilkinson, G. (1995). Transition Metal Arene Complexes: Nucleophilic Addition, Comprehensive Organometallic Chemistry II, Pergamon Press.","DOI":"10.1016\/B978-008046519-7.09005-5"},{"key":"ref_11","doi-asserted-by":"crossref","unstructured":"Astruc, D. (2002). Modern Arene Chemistry, Wiley. Chapter 11.","DOI":"10.1002\/3527601767"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"3722","DOI":"10.1002\/anie.200301634","article-title":"Metal Carbonyls: A New Class of Pharmaceuticals?","volume":"42","author":"Jonson","year":"2003","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"361","DOI":"10.1021\/ar00031a002","article-title":"Bioorganometallic Chemistry: A Future Direction for Transition Metal Organometallic Chemistry?","volume":"26","author":"Jaouen","year":"1993","journal-title":"Acc. Chem. Res."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Hess, A., and Metzler-Nolte, N. (1999). Transition metal labels on peptide nucleic acid (PNA) monomers. Chem. Commun., 885\u2013886.","DOI":"10.1039\/a901561b"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"4341","DOI":"10.1021\/ol026994a","article-title":"Synthesis of Chiral Chromium Tricarbonyl Labeled Thymine PNA Monomers via the Ugi Reaction","volume":"4","author":"Baldoli","year":"2002","journal-title":"Org. Lett."},{"key":"ref_16","first-page":"953","article-title":"Synthesis of o- and m-carboranylbenzenechromotricarbonyls by the reaction of lithium o- and m-carboranes with chlorobenzenechromotricarbonyl","volume":"53","author":"Zakharkin","year":"1983","journal-title":"Zhurnal Obshchei Khimii"},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"Vasyukova, N.I., Nekrasov, Y.S., Sukharev, Y.N., Magomedov, G.K., and Frenkel, A.S. (1985). Mass spectrometry of \u03c0-complexes of transition metals. 33. Carboranyl derivatives of benzenechromium tricarbonyl. Izvestiya Akademii Nauk SSSR Seriya Khimicheskaya, 1548\u20131549.","DOI":"10.1007\/BF00950141"},{"key":"ref_18","doi-asserted-by":"crossref","unstructured":"Magomedov, G.K., Frenkel, A.S., Kalinin, V.N., and Zakharkin, L.I. (1977). Synthesis of arylcarboranechromiumtricarbonyls. Izvestiya Akademii Nauk SSSR Seriya Khimicheskaya, 949\u2013952.","DOI":"10.1002\/chin.197734314"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"8569","DOI":"10.1021\/ic0509736","article-title":"1,2-Dicarba-closo-dodecaboran-1-yl Naphthalene Derivatives","volume":"44","author":"Ohta","year":"2005","journal-title":"Inorg. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"6463","DOI":"10.1021\/ma100792z","article-title":"Poly(\u03b3-glutamic acid) Hydrogels with Water-Sensitive Luminescence Derived from Aggregation-Induced Emission of o-Carborane","volume":"43","author":"Kokado","year":"2010","journal-title":"Macromolecules"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"2313","DOI":"10.1021\/om00042a057","article-title":"Reactions of Anionic Carborane Nucleophiles with Chromium-Coordinated Haloarenes","volume":"11","author":"Henly","year":"1992","journal-title":"Organometallics"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"154","DOI":"10.1002\/9780470132500.ch35","article-title":"(\u03b76-Arene)tricarbonylchromium Complexes","volume":"19","author":"Mahaffy","year":"1979","journal-title":"Inorg. Synth."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"165","DOI":"10.1002\/cber.19600930127","article-title":"IR-spektroskopische Untersuchungen der \u03bd-CO-Banden an Metallcarbonylkomplexen rnit zentrisch-x-gebundenen organischen Ringsystemen","volume":"93","author":"Fischer","year":"1960","journal-title":"Chem. Ber."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Brown, D.A., and Sloan, H. (1963). Molecular-orbital Theory of Organometallic Compounds. Part I V.l Substitution Reactions of Tricarbonylbenzenechromium. J. Chem. Soc., 4389\u20134394.","DOI":"10.1039\/jr9630004389"},{"key":"ref_25","doi-asserted-by":"crossref","unstructured":"Brown, D.A., and Raju, J.R. (1966). Infrared and Proton Magnetic Resonance Spectra of \u03c0-Complexes of Substituted Condensed Hydrocarbons. J. Chem. Soc. A., 1617\u20131620.","DOI":"10.1039\/J19660001617"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"558","DOI":"10.1039\/DT9740000558","article-title":"Vibrational Spectra of Some Monosubstituted-\u03c0-arene Tricarbonylchromium Complexes and of Methyl Benzoate","volume":"6","author":"Adams","year":"1974","journal-title":"J. Chem. Soc. Dalton Trans."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"2372","DOI":"10.1039\/b700110j","article-title":"Carborane radical anions: Spectroscopic and electronic properties of a carborane radical anion with a 2n + 3 skeletal electron count","volume":"23","author":"Fox","year":"2007","journal-title":"Chem. Commun."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2786","DOI":"10.1039\/B406422D","article-title":"Exo-\u03c0-bonding to an ortho-carborane hypercarbon atom: Systematic icosahedral cage distortions reflected in the structures of the fluoro-, hydroxy- and amino-carboranes, 1-X-2-Ph-1,2-C2B10H10 (X = F, OH or NH2) and related anions","volume":"17","author":"Boyd","year":"2004","journal-title":"Dalton Trans."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2359","DOI":"10.1016\/j.poly.2009.04.041","article-title":"Trends in ortho-carboranes 1-X-2-R-1,2-C2B10H10 (R = Ph, Me) bearing an exo-CN-bonded substituent group (X = NO, N=NR\u02b9 or NHR\u02ba)","volume":"28","author":"Fox","year":"2009","journal-title":"Polyhedron"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"705","DOI":"10.1107\/S0108270192012125","article-title":"Structure of 1,2-Diphenylcarbaborane, 1,2-Ph2-1,2-closo-C2B10H10","volume":"49","author":"Lewis","year":"1993","journal-title":"Acta Crystallogr. Sect. C."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"305","DOI":"10.1016\/S0022-328X(00)99158-7","article-title":"Metal-Carbon \u201cBond Strengths\u201d in Cr(CO)6, Cr(\u03b7-C6H6)2, and Cr(CO)3(\u03b7-C6H6)","volume":"262","author":"Calhorda","year":"1984","journal-title":"J. Organomet. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2516","DOI":"10.1107\/S0567740873006941","article-title":"Electronic Structure of Benzene Chromium Tricarbonyl by X-ray and Neutron Diffraction at 78 \u00baK","volume":"29","author":"Rees","year":"1973","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1314","DOI":"10.1021\/ic50031a017","article-title":"Three-Dimensional Crystal Structure of Benzenechromium Tricarbonyl with Further Comments on the Dibenzenechromium Structure","volume":"4","author":"Bailey","year":"1965","journal-title":"Inorg. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"587","DOI":"10.1021\/ja00236a050","article-title":"Redetermination of the Experimental Electron Deformation Density of Benzenetricarbonylchromium","volume":"109","author":"Wang","year":"1987","journal-title":"J. Am. Chem. Soc."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"9439","DOI":"10.1039\/c1dt10994d","article-title":"Haptotropic rearrangement in tricarbonylchromium complexes of 2-aminobiphenyl and 4-aminobiphenyl","volume":"40","author":"Czerwinski","year":"2011","journal-title":"Dalton Trans."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"638","DOI":"10.1107\/S2053229617010774","article-title":"Intricacies of ligand coordination in tricarbonylchromium(0) complexes with ortho- and para-fluorobiphenyls","volume":"73","author":"Guzei","year":"2017","journal-title":"Acta Crystallogr. Sect. C"},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Davidson, M.G., Hibbert, T.G., Howard, J.A.K., Mackinnon, A., and Wade, K. (1996). Definitive crystal structures of ortho-, meta- and para-carboranes: Supramolecular structures directed solely by C\u2212H\u00b7\u00b7\u00b7O hydrogen bonding to hmpa (hmpa = hexamethylphosporamide). Chem. Commun., 2285\u20132286.","DOI":"10.1039\/CC9960002285"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"232","DOI":"10.1016\/S0022-328X(02)01637-6","article-title":"Modulation of the C\u2212C distance in disubstituted 1,2-R2-o-carboranes. Crystal structure of closo 1,2-(SPh)2-1,2-C2B10H10","volume":"657","author":"Llop","year":"2002","journal-title":"J. Organomet. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"13538","DOI":"10.1021\/ja052091b","article-title":"Strikingly Long C\u00b7\u00b7\u00b7C Distances in 1,2-Disubstituted ortho-Carboranes and Their Dianions","volume":"127","author":"Oliva","year":"2005","journal-title":"J. Am. Chem. Soc."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"5345","DOI":"10.1039\/b810702e","article-title":"Unprecedented steric deformation of ortho-carborane","volume":"42","author":"Hutton","year":"2008","journal-title":"Chem. Commun."},{"key":"ref_41","unstructured":"(2002). Bruker Analytical X-ray Division, SMART and SAINT, Bruker."},{"key":"ref_42","unstructured":"Sheldrick, G.M. (2002). Bruker Analytical X-Ray Division, SHELXTL-PLUS Software Package, Bruker."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/13\/4942\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T19:59:21Z","timestamp":1760126361000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/13\/4942"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,6,23]]},"references-count":42,"journal-issue":{"issue":"13","published-online":{"date-parts":[[2023,7]]}},"alternative-id":["molecules28134942"],"URL":"https:\/\/doi.org\/10.3390\/molecules28134942","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,6,23]]}}}