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Subsequent reaction of Ag[BCNB] with Ni(CO)4 yields the first structurally characterized complex in which Ni(CO)4 coordinates to a transition-metal ion, demonstrating the exceptionally low basicity of this anion.",{"@graph":14,"@context":72},[15,34,55],{"@type":16,"itemListElement":17},"BreadcrumbList",[18,23,27,31],{"item":19,"name":20,"@type":21,"position":22},"https://docshare.wps.com","Home","ListItem",1,{"item":24,"name":25,"@type":21,"position":26},"https://docshare.wps.com/document/","Document",2,{"item":28,"name":29,"@type":21,"position":30},"https://docshare.wps.com/document/research-report/","Research & 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is the Ag[BCNB] salt prepared in this work?","Question",{"text":62,"@type":63},"AgCN is reacted with two equivalents of BCF in CH2Cl2 or orthodifluorobenzene to produce solvated Ag+ salts of the cyanide-bridged weakly coordinating anion [m-(CN)(BCF)2]− (BCNB).","Answer",{"name":65,"@type":60,"acceptedAnswer":66},"What is the role of Ni(CO)4 in the reported coordination chemistry?",{"text":67,"@type":63},"Ni(CO)4 reacts with Ag[BCNB] to form a structurally characterized complex where Ni(CO)4 acts as a ligand towards the transition-metal ion, highlighting the very low basicity of the BCNB anion.",{"name":69,"@type":60,"acceptedAnswer":70},"Why is this method considered important compared with previous approaches?",{"text":71,"@type":63},"The paper targets a readily accessible silver salt with a very weakly coordinating counter anion synthesized in weakly basic solvents, enabling structural characterization that was previously elusive despite IR indications.","https://schema.org",{"og:url":32,"og:type":74,"og:title":10,"og:site_name":45,"og:description":12},"article",{"robots":76,"canonical":32},"index,follow",{"doc_id":78,"site_id":7},450018,1791254472,{"code":4,"msg":81,"data":82},"success",[83,87,91,95,100,105,110,114,119,122,126],{"id":22,"doc_module":4,"doc_module_name":25,"category_name":84,"show_sort_weight":85,"slug":86},"Story & 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.1039/d5sc05589j  \nAll publication charges for this article have been paid for by the Royal Society of Chemistry  \nReceived 25th July 2025  \nAccepted 5th November 2025 DOI: 10.1039/d5sc05589j[rsc.li/chemical-science](rsc.li/chemical-science)  \nA facile route to ‘naked’ Ag+ ions enabling the coordination of the weak Lewis base Ni(CO)4  \nWilli R. Berg,a Amina L. Moshtaha,a Robin Sievers,a Marc Reimann,  bc Tim-Niclas Streit,a Susanne M. Rupf,  a Martin Kaupp  band Moritz Malischewski  *a  \nThe reaction of AgCN with two equivalents of tris(pentafluorophenyl)borane (BCF) in CH2Cl2 or orthodifluorobenzene (o DFB) provides a straightforward access to (solvated) Ag+ salts of the weakly coordinating cyanide-bridged anion [m-(CN)(BCF)2] − (suggested abbreviation [BCNB]) . Reacting Ag [BCNB] with Ni(CO)4 yields the first structurally characterized complex in which Ni(CO)4 acts as a ligand towards a transition metal ion proving the extremely low basicity of the anion.  \nIntroduction  \nChemically robust, weakly coordinating anions (WCAs) are essential to stabilize reactive cations in both the solution phase as well as in the solid state.1,2 When selecting an appropriate WCA, key factors to consider are their oxidative stability,3 electrophilic stability4 and low coordination ability.5 O􀀁en these properties are achieved by delocalization of the negative charge over a large non-nucleophilic and chemically robust moiety.2 Common WCAs such as borate anions [BF4] − ,6 and hexa-􀀁uorometalates [MF6] − (M = As, Sb; and their respective oligomeric structures) are well established.7,8 However, they can act as ligands towards highly electrophilic metal centers.9 In contrast, “designer” WCAs with improved properties are typically not commercially available and require multi-step syntheses e.g. te􀀁ate-based anions10 or poly-/per􀀁uoro alkoxymetalates.11–13 In recent years, [Al(OC(CF3)3)4] − (Fig. 1) showed its effectiveness in stabilizing highly reactive cations.14 A multi-step synthesis is required to access its silver salt by salt metathesis of the corresponding Li+ salt in liquid SO2 (boiling point −10 °C) .11,12 However, employing such anions enabled the isolation of complexes where two neutral homoleptic transition metal carbonyls such as Fe(CO)5 act as ligands towards coinage metals Cu+/Ag+/Au+ .15–18 Anions such as [SbF6] − or [B{3,5-(CF3)2C6H3}4] − also stabilize the corresponding monosubstituted Fe(CO)5 coinage metal adducts,19–21 as well as [Hg {Fe(CO)5}2]2+ .22 Besides mononuclear Fe(CO)5 and M(CO)6 (M = W, Mo, Nb, Ta)23,24 clustered zerovalent homoleptic transition  \naInstitute of Chemistry and Biochemistry, Inorganic Chemistry, Freie Universitt Berlin, Fabeckstr. 34–36, 14195 Berlin, Germany. E-mail: moritz.malischewski@ [fu-berlin.de](fu-berlin.de)  \nbInstitut für Chemie, Theoretische Chemie/Quantenchemie Sekr. C7, Technische Universitt Berlin, Straße des 17. Juni 135, 10623 Berlin, Germany  \nc Universitt Innsbruck, Institut für Ionenphysik undAngewandte Physik, Technikerstr. 25/3, 6020 Innsbruck, Austria  \nmetal carbonyls (Re2(CO)10, M3(CO)12 with M = Ru, Os and  \nIr4(CO)12) were successfully coordinated to Ag+ as well.25–27  \nAs indicated by the signi􀀃cantly lower proton affinity of Ni(CO)4 (718 kJ mol−1, B3LYP-D3(BJ)/def2-TZVPP) in comparison to Fe(CO)5 (815 kJ mol−1),8 use of Ni(CO)4 has so far not allowed the structural characterization of a corresponding metal complex in which it acts as a Lewis base although IR spectroscopy hinted to a potential coordination of Ni(CO)4 to Ag+[FAl(OC(CF3)3)] − but the potential adduct could neither be isolated in pure form nor crystallized.28 To achieve this, a readily available silver salt with a very weakly coordinating counter anion, which can be synthesized in weakly basic solvents, is necessary. In this context, anions derived from 􀀁uorinated  \nFig. 1 Selected examples of Ag[WCA] salts. (a) Multi-step synthesis procedures required. (b) Not stable a","cbCaihfuDcUnj27m","https://ap.wps.com/l/cbCaihfuDcUnj27m","pdf",766048,"English","# Introduction\n## Weakly coordinating anions and design requirements\n## Limitations of existing anions and prior nickel(I) coordination attempts\n# Results and discussion","[{\"question\":\"How is the Ag[BCNB] salt prepared in this work?\",\"answer\":\"AgCN is reacted with two equivalents of BCF in CH2Cl2 or orthodifluorobenzene to produce solvated Ag+ salts of the cyanide-bridged weakly coordinating anion [m-(CN)(BCF)2]− (BCNB).\"},{\"question\":\"What is the role of Ni(CO)4 in the reported coordination chemistry?\",\"answer\":\"Ni(CO)4 reacts with Ag[BCNB] to form a structurally characterized complex where Ni(CO)4 acts as a ligand towards the transition-metal ion, highlighting the very low basicity of the BCNB anion.\"},{\"question\":\"Why is this method considered important compared with previous approaches?\",\"answer\":\"The paper targets a readily accessible silver salt with a very weakly coordinating counter anion synthesized in weakly basic solvents, enabling structural characterization that was previously elusive despite IR indications.\"}]","A facile route to ‘naked’ Ag+ ions enabling the coordination of the weak Lewis base Ni(CO)4 | PDF",1790731835,15]