{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,11,12]],"date-time":"2026-11-12T02:17:39Z","timestamp":1794449859683,"version":"4.9.1"},"reference-count":81,"publisher":"American Chemical Society (ACS)","issue":"31","license":[{"start":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T00:00:00Z","timestamp":1785369600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/V034766\/1"],"award-info":[{"award-number":["EP\/V034766\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/W00691X\/1"],"award-info":[{"award-number":["EP\/W00691X\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100031478","name":"NextGenerationEU","doi-asserted-by":"publisher","award":["P2022PZ8JE"],"award-info":[{"award-number":["P2022PZ8JE"]}],"id":[{"id":"10.13039\/100031478","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,11]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>This study describes the synthesis, characterization, and preliminary antimicrobial investigation of a series of rollover platinum complexes derived from 6-chloro-2,2\u2032-bipyridine (bpyCl) and 6-bromo-2,2\u2032-bipyridine (bpyBr) ligands. The electron-withdrawing halogen substituents in the 6-position significantly influence the coordination behavior of the ligands, favoring \u201crollover\u201d cyclometalation rather than conventional N^N chelation. A series of platinum complexes, including [Pt(bpyX-H)(DMSO)Me], [Pt(bpyX-H)(PPh3)Me], [Pt(bpyX-H)(DMSO)Cl], [Pt(bpyX-H)(PPh3)Cl] (where X = Br or Cl), were successfully synthesized and characterized using multinuclear NMR spectroscopy and, in two cases, X-ray crystallography. The ligands\u2019 stereoelectronic profile was evaluated based on the steric hindrance of the substituents and the electronic properties of the nitrogen donors. Electronic donor properties were correlated with NMR coupling constant data of the complexes. The reduced Lewis basicity of these ligands results in a noticeable reluctance to adopt the traditional N^N chelation motif; this is substantiated by the X-ray crystal structure of the complex [Pt(bpyBr)Cl2], which reveals a severe distortion induced by the bromine substituent. Conversely, a pronounced inclination toward rollover cyclometalation was observed. Selected complexes were thoroughly characterized and subsequently evaluated in a preliminary investigation of their antimicrobial activity against a panel of Gram-positive and Gram-negative multidrug-resistant bacteria, as well as a representative yeast strain, selected among clinically relevant and high-priority pathogens. Antibiofilm activity was also assessed, revealing moderate broad-spectrum antimicrobial effects and promising antibiofilm performance. These findings provide a useful basis for future structure\u2013activity relationship studies and further optimization of the compounds. Furthermore, the reactivity of these species was also explored, leading to the isolation of various derivatives, including rare acetimine complexes obtained via room-temperature activation of ammonia and acetone.<\/jats:p>","DOI":"10.1021\/acsomega.6c05687","type":"journal-article","created":{"date-parts":[[2026,8,4]],"date-time":"2026-08-04T13:20:07Z","timestamp":1785849607000},"page":"47011-47031","source":"Crossref","is-referenced-by-count":2,"title":["Pt(II) Rollover\nComplexes with Poor-Donor Bipyridines:\nSynthesis, Reactivity, and Preliminary Antimicrobial Evaluation"],"prefix":"10.1021","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4423-9382","authenticated-orcid":true,"given":"Antonio","family":"Zucca","sequence":"first","affiliation":[{"name":"University of Sassari , , Via Vienna 2 , ,","place":["Sassari, Italy, I-07100"]},{"name":"Consorzio Interuniversitario Reattivita\u0300 Chimica e Catalisi (CIRCC) , ,","place":["Bari, Italy, 70126"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matteo","family":"Murineddu","sequence":"additional","affiliation":[{"name":"University of Sassari , , Via Vienna 2 , ,","place":["Sassari, Italy, I-07100"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1743-8338","authenticated-orcid":true,"given":"Fabrizio","family":"Ortu","sequence":"additional","affiliation":[{"name":"University of Leicester , , University Road , ,","place":["Leicester, U.K., LE1 7RH"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yu","family":"Liu","sequence":"additional","affiliation":[{"name":"University of Leicester , , University Road , ,","place":["Leicester, U.K., LE1 7RH"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gabriele","family":"Manca","sequence":"additional","affiliation":[{"name":"c\/o Universita\u0300 Degli Studi di Bari \u201cAldo Moro\u201d , , Via Orabona 4 , ,","place":["Bari, Italy, 70126"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Germano","family":"Orru\u0300","sequence":"additional","affiliation":[{"name":"University of Cagliari , , ,","place":["Cagliari, Italy, 09124"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alessandra","family":"Scano","sequence":"additional","affiliation":[{"name":"University of Cagliari , , ,","place":["Cagliari, Italy, 09124"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maria I.","family":"Pilo","sequence":"additional","affiliation":[{"name":"University of Sassari , , Via Vienna 2 , ,","place":["Sassari, Italy, I-07100"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,30]]},"reference":[{"issue":"11\u201312","key":"2026081110190504400_cit1","doi-asserted-by":"publisher","first-page":"995","DOI":"10.1016\/j.ccr.2004.05.011","article-title":"Intramolecular\nFive-Membered Ring Compounds and Their Applications","volume":"248","author":"Omae","year":"2004","journal-title":"Coord. 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Chem."},{"issue":"44","key":"2026081110190504400_cit5","doi-asserted-by":"publisher","first-page":"15633","DOI":"10.1039\/D0DT02224A","article-title":"The Synthesis of Cyclometalated\nPlatinum(ii) Complexes with\nBenzoaryl-Pyridines as C^N Ligands for Investigating Their Photophysical,\nElectrochemical and Electroluminescent Properties","volume":"49","author":"Wang","year":"2020","journal-title":"Dalton Trans."},{"issue":"4","key":"2026081110190504400_cit6","doi-asserted-by":"publisher","first-page":"437","DOI":"10.2174\/0929867324666170529125229","article-title":"Cyclometalated\nComplexes of Platinum\nand Gold with Biological Properties: State-of-the-Art and Future Perspectives","volume":"25","author":"Jurgens","year":"2018","journal-title":"CMC"},{"issue":"21","key":"2026081110190504400_cit7","doi-asserted-by":"publisher","first-page":"2776","DOI":"10.2174\/1385272819666141013224601","article-title":"Unconventional\nCyclometalation Reactions","volume":"18","author":"Omae","year":"2014","journal-title":"Curr. 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Chem."},{"issue":"19","key":"2026081110190504400_cit15","doi-asserted-by":"publisher","first-page":"5402","DOI":"10.1021\/om500712e","article-title":"Carbon-Hydrogen\nversus Nitrogen-Oxygen\nBond Activation in Reactions of N-Oxide Derivatives of 2,2\u2032-Bipyridine\nand 1,10-Phenanthroline with a Dimethylplatinum(II) Complex","volume":"33","author":"Moustafa","year":"2014","journal-title":"Organometallics"},{"issue":"I","key":"2026081110190504400_cit16","doi-asserted-by":"publisher","first-page":"4784","DOI":"10.1002\/ejic.201901116","article-title":"Theoretical\nand Spectroscopic Characterisation\nof a Series of Novel Gold(I)-Norbornene Complexes Supported by Phenanthrolines:\nEffects of the Supporting Ligand","volume":"2019","author":"Cinellu","year":"2019","journal-title":"Eur. J. Inorg.\nChem."},{"issue":"13","key":"2026081110190504400_cit17","doi-asserted-by":"publisher","first-page":"2680","DOI":"10.1039\/B303297C","article-title":"Chemical\nand Biological Studies of the Dichloro(2-Phenylpyridine) Gold(iii)\nComplex and Its Derivatives","author":"Fan","year":"2003","journal-title":"Dalton Trans."},{"issue":"18","key":"2026081110190504400_cit18","doi-asserted-by":"publisher","first-page":"4046","DOI":"10.1021\/ic990238s","article-title":"Probing\nd8 \u2013 d8 Interactions in Luminescent Mono-\nand Binuclear Cyclometalated Platinum(II) Complexes of 6-Phenyl-2,2\u2018-Bipyridines","volume":"38","author":"Lai","year":"1999","journal-title":"Inorg. Chem."},{"issue":"21","key":"2026081110190504400_cit19","doi-asserted-by":"publisher","first-page":"3951","DOI":"10.3390\/molecules24213951","article-title":"The Early\nYears of 2,2\u2019-Bipyridine \u2500\nA Ligand in Its Own Lifetime","volume":"24","author":"Constable","year":"2019","journal-title":"Molecules"},{"issue":"13","key":"2026081110190504400_cit20","doi-asserted-by":"publisher","first-page":"3414","DOI":"10.1021\/om5003057","article-title":"Synthesis and Characterization\nof\nPalladium(II) and Platinum(II) Adducts and Cyclometalated Complexes\nof 6,6\u2032-Dimethoxy-2,2\u2032-Bipyridine: C(Sp3)\u2013H\nand C(Sp2)\u2013H Bond Activations","volume":"33","author":"Cocco","year":"2014","journal-title":"Organometallics"},{"issue":"14","key":"2026081110190504400_cit21","doi-asserted-by":"publisher","first-page":"3415","DOI":"10.1021\/om800027g","article-title":"C \u201cRollover\u201d\nCyclometalated Platinum(II) Hydrides: Mono- and Polynuclear Derivatives","volume":"27","author":"Minghetti","year":"2008","journal-title":"Organometallics"},{"issue":"9","key":"2026081110190504400_cit22","doi-asserted-by":"publisher","first-page":"2253","DOI":"10.1021\/om051075k","article-title":"Dinuclear\nC,N,C Cyclometalated Platinum Derivatives with Bridging Delocalized\nLigands. Fourfold Deprotonation of 6,6\u2018-Diphenyl-2,2\u2018-Bipyridine,\nH4 L, Promoted by \u201cPt(R)2\u201d Fragments\n(R = Me, Ph). Crystal Structures of [Pt2 (L)(3,5-Me2 Py)2] and {Pt2 (L)(Dppe)}2 (Dppe = 1,2-Bis(Diphenylphosphino)Ethane). X-Ray Powder Diffraction\nof [Pt2 (L)(CO)2]","volume":"25","author":"Zucca","year":"2006","journal-title":"Organometallics"},{"issue":"43","key":"2026081110190504400_cit23","doi-asserted-by":"publisher","first-page":"4884","DOI":"10.1039\/b705079h","article-title":"Some Uses of Transition\nMetal Complexes as Anti-Cancer and Anti-HIV Agents","author":"Wai-Yin Sun","year":"2007","journal-title":"Dalton Trans."},{"issue":"23","key":"2026081110190504400_cit24","doi-asserted-by":"publisher","first-page":"14852","DOI":"10.1021\/acs.inorgchem.8b02604","article-title":"New Variations\non the Theme of Gold(III)\nC \u2227 N \u2227 N Cyclometalated Complexes as Anticancer Agents:\nSynthesis and Biological Characterization","volume":"57","author":"Carboni","year":"2018","journal-title":"Inorg.\nChem."},{"issue":"22","key":"2026081110190504400_cit25","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202218000","article-title":"Gold Complexes in Anticancer Therapy:\nFrom New Design Principles to Particle-Based Delivery Systems","volume":"62","author":"Moreno-Alca\u0301ntar","year":"2023","journal-title":"Angew. 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Resist."},{"issue":"3","key":"2026081110190504400_cit32","doi-asserted-by":"publisher","first-page":"202","DOI":"10.1038\/s41570-023-00463-4","article-title":"Metals\nto Combat Antimicrobial Resistance","volume":"7","author":"Frei","year":"2023","journal-title":"Nat. Rev.\nChem."},{"issue":"3","key":"2026081110190504400_cit33","doi-asserted-by":"publisher","first-page":"545","DOI":"10.1007\/s10534-023-00565-y","article-title":"The Good,\nthe Bad, and the Ugly of Metals as Antimicrobials","volume":"37","author":"Turner","year":"2024","journal-title":"BioMetals"},{"key":"2026081110190504400_cit34","doi-asserted-by":"publisher","first-page":"102347","DOI":"10.1016\/j.mib.2023.102347","article-title":"Recent Advances in\nthe Development of Metal Complexes as Antibacterial Agents with Metal-Specific\nModes of Action","volume":"75","author":"Waters","year":"2023","journal-title":"Curr. Opin. Microbiol."},{"key":"2026081110190504400_cit35","doi-asserted-by":"publisher","first-page":"188","DOI":"10.1016\/j.jinorgbio.2017.02.015","article-title":"[Au(Pyb-H)(Mnt)]: A\nNovel Gold(III) 1,2-Dithiolene Cyclometalated\nComplex with Antimicrobial Activity (Pyb-H = C-Deprotonated 2-Benzylpyridine;\nMnt = 1,2-Dicyanoethene-1,2-Dithiolate)","volume":"170","author":"Pintus","year":"2017","journal-title":"J.\nInorg. Biochem."},{"key":"2026081110190504400_cit36","doi-asserted-by":"publisher","DOI":"10.1007\/978-94-009-5883-8","volume-title":"pKa Prediction for\nOrganic Acids and Bases","author":"Perrin","year":"1981"},{"key":"2026081110190504400_cit37","unstructured":"pKa Data Compiled By R. 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Ref.\nData"},{"issue":"14","key":"2026081110190504400_cit39","doi-asserted-by":"publisher","first-page":"1698","DOI":"10.1021\/acs.organomet.6c00114","article-title":"Pt (II) Rollover Cyclometalated Complexes Supported by 2,2\u2019-Bipyridine\nN-Oxide: Synthesis, Characterisation and Biological Evaluation","volume":"45","author":"Zucca","year":"2026","journal-title":"Organometallics"},{"issue":"5","key":"2026081110190504400_cit40","doi-asserted-by":"publisher","first-page":"1064","DOI":"10.1021\/om1000474","article-title":"Intramolecular\nC(Sp2)\u2013H\nBond Activation in 6,6\u2032-Dimethoxy-2,2\u2032-Bipyridine with\nGold(III). Crystal and Molecular Structure of the First N\u2032,C(3)\n\u201cRollover\u201d Cycloaurated Derivative","volume":"29","author":"Cocco","year":"2010","journal-title":"Organometallics"},{"issue":"4","key":"2026081110190504400_cit41","doi-asserted-by":"publisher","first-page":"380","DOI":"10.1021\/jacsau.0c00104","article-title":"Rollover Cyclometalation\nvs Nitrogen Coordination in Tetrapyridyl Anticancer Gold(III) Complexes:\nEffect on Protein Interaction and Toxicity","volume":"1","author":"Zhou","year":"2021","journal-title":"JACS Au"},{"issue":"9","key":"2026081110190504400_cit42","doi-asserted-by":"publisher","first-page":"609","DOI":"10.1039\/C39850000609","article-title":"\u201cRoll-over\u201d 3-Metallation\nof Co-Ordinated 2,2\u2032-Bipyridyl in the Thermal Rearrangement\nof Diaryl(Bipyridyl)Platinum(II) Complexes: Molecular Structure of\n(\u03bc-Bidyl)[PtPh(Butpy)]2","author":"Skapski","year":"1985","journal-title":"J. Chem. Soc.,\nChem. 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