{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T20:23:33Z","timestamp":1760300613745,"version":"build-2065373602"},"reference-count":48,"publisher":"MDPI AG","issue":"13","license":[{"start":{"date-parts":[[2021,6,26]],"date-time":"2021-06-26T00:00:00Z","timestamp":1624665600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001659","name":"Deutsche Forschungsgemeinschaft","doi-asserted-by":"publisher","award":["Sche 384\/36-1"],"award-info":[{"award-number":["Sche 384\/36-1"]}],"id":[{"id":"10.13039\/501100001659","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>By reacting [{Cp\u2034Fe(CO)2}2(\u00b5,\u03b71:1-P4)] (1) with in situ generated phosphenium ions [Ph2P][A] ([A]\u2212 = [OTf]\u2212 = [O3SCF3]\u2212, [PF6]\u2212), a mixture of two main products of the composition [{Cp\u2034Fe(CO)2}2(\u00b5,\u03b71:1-P5(C6H5)2)][PF6] (2a and 3a) could be identified by extensive 31P NMR spectroscopic studies at 193 K. Compound 3a was also characterized by X-ray diffraction analysis, showing the rarely observed bicyclo[2.1.0]pentaphosphapentane unit. At room temperature, the novel compound [{Cp\u2034Fe}(\u00b5,\u03b74:1-P5Ph2){Cp\u2034(CO)2Fe}][PF6] (4) is formed by decarbonylation. Reacting 1 with in situ generated diphenyl arsenium ions gives short-lived intermediates at 193 K which disproportionate at room temperature into tetraphenyldiarsine and [{Cp\u2034Fe(CO)2}4(\u00b54,\u03b71:1:1:1-P8)][OTf]2 (5) containing a tetracyclo[3.3.0.02,7.03,6]octaphosphaoctane ligand.<\/jats:p>","DOI":"10.3390\/molecules26133920","type":"journal-article","created":{"date-parts":[[2021,6,27]],"date-time":"2021-06-27T23:57:22Z","timestamp":1624838242000},"page":"3920","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Insertion of Phosphenium Ions into a Bicyclo[1.1.0]Tetraphosphabutane Iron Complex"],"prefix":"10.3390","volume":"26","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8266-9669","authenticated-orcid":false,"given":"Martin","family":"Weber","sequence":"first","affiliation":[{"name":"Institute of Inorganic Chemistry, University of Regensburg, Universit\u00e4tsstrasse 31, 93040 Regensburg, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"G\u00e1bor","family":"Bal\u00e1zs","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry, University of Regensburg, Universit\u00e4tsstrasse 31, 93040 Regensburg, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8843-8503","authenticated-orcid":false,"given":"Alexander V.","family":"Virovets","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry, University of Regensburg, Universit\u00e4tsstrasse 31, 93040 Regensburg, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9870-9928","authenticated-orcid":false,"given":"Eugenia","family":"Peresypkina","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry, University of Regensburg, Universit\u00e4tsstrasse 31, 93040 Regensburg, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2182-5020","authenticated-orcid":false,"given":"Manfred","family":"Scheer","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry, University of Regensburg, Universit\u00e4tsstrasse 31, 93040 Regensburg, Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2021,6,26]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"4164","DOI":"10.1021\/cr9003709","article-title":"Early-transition-metal-mediated activation and transformation of white phosphorus","volume":"110","author":"Cossairt","year":"2010","journal-title":"Chem. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"4236","DOI":"10.1021\/cr100010e","article-title":"P4 activation by main group elements and compounds","volume":"110","author":"Scheer","year":"2010","journal-title":"Chem. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"4178","DOI":"10.1021\/cr900349u","article-title":"P4 activation by late-transition metal complexes","volume":"110","author":"Caporali","year":"2010","journal-title":"Chem. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"2169","DOI":"10.1039\/c2cc17449a","article-title":"Activation of phosphorus by group 14 elements in low oxidation states","volume":"48","author":"Khan","year":"2012","journal-title":"Chem. Commun."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"350","DOI":"10.1002\/open.201700027","article-title":"Metalate-Mediated Functionalization of P4 by Trapping Anionic Cp*Fe(CO)2(\u03b71-P4)\u2212 with Lewis Acids","volume":"6","author":"Borger","year":"2017","journal-title":"ChemistryOpen"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2082","DOI":"10.1021\/ja00737a059","article-title":"Rhodium complexes with the molecular unit P4 as a ligand","volume":"93","author":"Ginsberg","year":"1971","journal-title":"J. Am. Chem. Soc."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"4110","DOI":"10.1021\/om9801148","article-title":"P4 Activation with [{Cp\u2034(OC)2Fe}2](Cp\u2034 = C5H2tBu3-1,2,4): Exclusive Formation of the Exo\/ Exo-Butterfly Complex [{Cp\u2034(OC)2Fe}2(\u03bc-\u03b71:\u03b71-P4)]","volume":"17","author":"Scherer","year":"1998","journal-title":"Organometallics"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"9077","DOI":"10.1002\/anie.201404653","article-title":"Selective Formation and Unusual Reactivity of Tetraarsabicyclo[1.1.0]butane Complexes","volume":"53","author":"Schwarzmaier","year":"2014","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2257","DOI":"10.1039\/D0CC08328C","article-title":"From a P4 butterfly scaffold to cyclo- and catena-P4 units","volume":"57","author":"Scheer","year":"2021","journal-title":"Chem. Commun."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"7312","DOI":"10.1002\/anie.201703175","article-title":"Rearrangement of a P4 Butterfly Complex-The Formation of a Homoleptic Phosphorus-Iron Sandwich Complex","volume":"56","author":"Heinl","year":"2017","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"120234","DOI":"10.1016\/j.ica.2020.120234","article-title":"The reactivity of the P4-butterfly ligand [{Cp\u2034Fe(CO)2}2(\u00b5,\u03b71:1-P4)] towards transition metal complexes: Coordination versus rearrangement","volume":"518","author":"Schwarzmaier","year":"2021","journal-title":"Inorg. Chim. Acta"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"13116","DOI":"10.1002\/anie.201506784","article-title":"E4 Butterfly Complexes (E = P, As) as Chelating Ligands","volume":"54","author":"Schwarzmaier","year":"2015","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3383","DOI":"10.1039\/D1CC00615K","article-title":"Reactivity of P4 butterfly complexes towards NHCs - generation of a metal-bridged P2 dumbbell complex","volume":"57","author":"Reichl","year":"2021","journal-title":"Chem. Commun."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"11722","DOI":"10.1002\/chem.202002957","article-title":"The Butterfly Complex {Cp*Cr(CO)3}2(\u03bc,\u03b71:1-P4) as a Versatile Ligand and Its Unexpected P1\/P3 Fragmentation","volume":"26","author":"Scheer","year":"2020","journal-title":"Chemistry"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1342","DOI":"10.1016\/j.ccr.2010.12.016","article-title":"Reactivity of white phosphorus with compounds of the p-block","volume":"255","author":"Giffin","year":"2011","journal-title":"Coord. Chem. Rev."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"295","DOI":"10.1002\/anie.200804903","article-title":"Formation of [Ph2P5]+, [Ph4P6]2+, and [Ph6P7]3+ Cationic Clusters by Consecutive Insertions of [Ph2P]+ into P-P Bonds of the P4 Tetrahedron","volume":"48","author":"Weigand","year":"2009","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"7947","DOI":"10.1021\/ja011075l","article-title":"Phosphine ligand exchange at a phosphine lewis acceptor: The first structural characterization of homoleptic phosphinophosphonium salts","volume":"123","author":"Burford","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"4712","DOI":"10.1021\/om9703595","article-title":"Structural Alternatives in R2(Cl)P: GaCl3 Systems (R = Alkyl, Phenyl), Including Examples of Intermolecular P \u2192 P Coordination","volume":"16","author":"Burford","year":"1997","journal-title":"Organometallics"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"28","DOI":"10.1002\/asia.200700229","article-title":"Catena-phosphorus cations","volume":"3","author":"Dyker","year":"2008","journal-title":"Chem. Asian J."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"6885","DOI":"10.1002\/ange.200602353","article-title":"A Melt Approach to the Synthesis ofcatena-Phosphorus Dications To Access Derivatives of [P6Ph4R4]2+","volume":"118","author":"Weigand","year":"2006","journal-title":"Angew. Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"7359","DOI":"10.1039\/c2cc33082b","article-title":"P-P Menschutkin preparation of prototypical phosphinophosphonium salts","volume":"48","author":"Chitnis","year":"2012","journal-title":"Chem. Commun."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"6639","DOI":"10.1039\/C4CS00019F","article-title":"The chemistry of cationic polyphosphorus cage\u2014Syntheses, structure and reactivity","volume":"43","author":"Holthausen","year":"2014","journal-title":"Chem. Soc. Rev."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"14404","DOI":"10.1021\/ja036649w","article-title":"Phosphine coordination complexes of the diphenylphosphenium cation: A versatile synthetic methodology for P-P bond formation","volume":"125","author":"Burford","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"17943","DOI":"10.1021\/ja907693f","article-title":"New synthetic procedures to catena-phosphorus cations: Preparation and dissociation of the first cyclo-phosphino-halophosphonium salts","volume":"131","author":"Weigand","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"4406","DOI":"10.1002\/1521-3773(20011203)40:23<4406::AID-ANIE4406>3.0.CO;2-X","article-title":"P5X2+ (X=Br, I), a Phosphorus-Rich Binary P-X Cation with a C(2v)-Symmetric P5 Cage","volume":"40","author":"Krossing","year":"2001","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"17165","DOI":"10.1002\/chem.202003291","article-title":"Cationic Functionalisation by Phosphenium Ion Insertion","volume":"26","author":"Riesinger","year":"2020","journal-title":"Chem. Eur. J."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"23879","DOI":"10.1002\/anie.202011571","article-title":"Stabilization of Pentaphospholes as \u03b75-Coordinating Ligands","volume":"59","author":"Riesinger","year":"2020","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"6106","DOI":"10.1021\/om700512h","article-title":"Triphenylphosphine-Stabilized Diphenyl-Arsenium, -Stibenium, and -Bismuthenium Salts","volume":"26","author":"Kilah","year":"2007","journal-title":"Organometallics"},{"doi-asserted-by":"crossref","unstructured":"Braddock, J.M.F., and Coates, G.E. (1961). 628. Arsinophosphonium salts. J. Chem. Soc., 3208\u20133211.","key":"ref_29","DOI":"10.1039\/jr9610003208"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"6380","DOI":"10.1021\/ic020410j","article-title":"Phosphine-stabilized arsenium salts: Water-stable, labile, coordination complexes","volume":"41","author":"Porter","year":"2002","journal-title":"Inorg. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"65","DOI":"10.1139\/v57-011","article-title":"The Analysis of Nuclear Magnetic Resonance Spectra: I. Systems of two and three Nuclei","volume":"35","author":"Bernstein","year":"1957","journal-title":"Can. J. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"18584","DOI":"10.1002\/anie.201908998","article-title":"Functionalization of Pentaphosphorus Cations by Complexation","volume":"58","author":"Adhikari","year":"2019","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"7858","DOI":"10.1002\/anie.201703953","article-title":"A Tetracyclic Octaphosphane by Successive Addition, Inversion, and Condensation Reactions","volume":"56","author":"Hennersdorf","year":"2017","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"3052","DOI":"10.1021\/ja00008a038","article-title":"Synthesis and structural-bonding analysis of [\u03b75-C5H4Me)4Fe4(CO)6P8] and [\u03b75-C5H4Me)4Fe6(CO)13P8]: Two unprecedented transition-metal complexes containing the cage-like P8 subunit of Hittorf\u2019s monoclinic phosphorus allotrope","volume":"113","author":"Barr","year":"1991","journal-title":"J. Am. Chem. Soc."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"15880","DOI":"10.1002\/anie.202005031","article-title":"Hierarchically Structured Allotropes of Phosphorus from Data-Driven Exploration","volume":"59","author":"Deringer","year":"2020","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"7702","DOI":"10.1002\/anie.201601775","article-title":"Unexpected Reactivity of (\u03b75-1,2,4-tBuC5H2)Ni(\u03b73-P3) towards Main Group Nucleophiles and by Reduction","volume":"55","author":"Peresypkina","year":"2016","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"721","DOI":"10.1002\/cber.19961290619","article-title":"Ir-Komplexe mit P4-Bicyclotetraphosphan und P8-Cunean als Liganden\u2014CO-Insertion in eine Ir\u2013P-Bindung","volume":"129","author":"Scheer","year":"1996","journal-title":"Chem. Ber."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"14592","DOI":"10.1021\/jacs.7b07704","article-title":"Selective Derivatization of a Hexaphosphane from Functionalization of White Phosphorus","volume":"139","author":"Hennersdorf","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"4340","DOI":"10.1002\/anie.201510716","article-title":"Influence of the nacnac Ligand in Iron(I)-Mediated P4 Transformations","volume":"55","author":"Spitzer","year":"2016","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"2216","DOI":"10.1039\/c2cc17638f","article-title":"P4 activation by group 3 metal arene complexes","volume":"48","author":"Huang","year":"2012","journal-title":"Chem. Commun."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"5740","DOI":"10.1021\/ja901045m","article-title":"{(\u03b75-C5Me5)2Sm}4P8: A molecular polyphosphide of the rare-earth elements","volume":"131","author":"Konchenko","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1932","DOI":"10.1002\/ejic.200400970","article-title":"Syntheses, Reactivity, and X-ray Structure Analyses of the Dimeric Pentaphosphides [(tBu3Si)3P5M2]2 (M = Na, Ag) and the Bicyclo[2.1.0]pentaphosphane (tBu3Si)3P5","volume":"2005","author":"Lerner","year":"2005","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"2972","DOI":"10.1002\/anie.201209329","article-title":"Ferrocene and pentaphosphaferrocene: A comparative study regarding redox chemistry","volume":"52","author":"Butovskiy","year":"2013","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"7643","DOI":"10.1002\/anie.201403581","article-title":"Functionalization of a cyclo-P5 ligand by main-group element nucleophiles","volume":"53","author":"Butovskii","year":"2014","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"490","DOI":"10.1002\/1521-3765(20010119)7:2<490::AID-CHEM490>3.0.CO;2-I","article-title":"The Facile Preparation of Weakly Coordinating Anions: Structure and Characterisation of Silverpolyfluoroalkoxyaluminates AgAl(ORF)4, Calculation of the Alkoxide Ion Affinity","volume":"7","author":"Krossing","year":"2001","journal-title":"Chem. Eur. J."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"951","DOI":"10.1002\/zaac.19966220606","article-title":"Eisen-Zweikernkomplexe mit unterschiedlichen P4-Liganden","volume":"622","author":"Scherer","year":"1996","journal-title":"Z. Anorg. Allg. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"2602","DOI":"10.1139\/v61-343","article-title":"Crystal data for diphenylarsenicals","volume":"39","author":"Cullen","year":"1961","journal-title":"Can. J. Chem."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"56","DOI":"10.1140\/epjp\/i2016-16056-0","article-title":"Status of the crystallography beamlines at PETRA III","volume":"131","author":"Burkhardt","year":"2016","journal-title":"Eur. Phys. J. Plus"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/13\/3920\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T06:24:53Z","timestamp":1760163893000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/26\/13\/3920"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,6,26]]},"references-count":48,"journal-issue":{"issue":"13","published-online":{"date-parts":[[2021,7]]}},"alternative-id":["molecules26133920"],"URL":"https:\/\/doi.org\/10.3390\/molecules26133920","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2021,6,26]]}}}