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Kelly, John A. ; Streitferdt, Verena ; Dimitrova, Maria ; Westermair, Franz F. ; Gschwind, Ruth Maria ; Berger, Rafael J. F. ; Wolf, Robert

Transition-Metal-Stabilized Heavy Tetraphospholide Anions

Kelly, John A., Streitferdt, Verena, Dimitrova, Maria , Westermair, Franz F. , Gschwind, Ruth Maria , Berger, Rafael J. F. und Wolf, Robert (2022) Transition-Metal-Stabilized Heavy Tetraphospholide Anions. Journal of the American Chemical Society 144 (44), S. 20434-20441.

Veröffentlichungsdatum dieses Volltextes: 04 Nov 2022 08:44
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.53155

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Zusammenfassung

Phosphorus analogues of the ubiquitous cyclopenta-dienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heavier group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopentadienyl anions SnP42-and ...

Phosphorus analogues of the ubiquitous cyclopenta-dienyl (Cp) are a rich and diverse family of compounds, which have found widespread use as ligands in organometallic complexes. By contrast, phospholes incorporating heavier group 14 elements (Si, Ge, Sn, and Pb) are hardly known. Here, we demonstrate the isolation of the first metal complexes featuring heavy cyclopentadienyl anions SnP42-and PbP42-. The complexes [(q4-tBu2C2P2)2Co2(mu,q5:q5- P4Tt)] [Tt = Sn (6), Pb (7)] are formed by reaction of white phosphorus (P4) with cyclooctadiene cobalt complexes [Ar ' TtCo(q4- P2C2tBu2)(q4-COD)] [Tt = Sn (2), Pb (3), Ar ' = C6H3-2,6{C6H3- 2,6-iPr2}2, COD = cycloocta-1,5-diene] and Tt{Co(q4-P2C2tBu2)-(COD)}2 [Tt = Sn (4), Pb (5)]. While the SnP42- complex 6 was isolated as a pure and stable compound, compound 7 eliminated Pb(0) below room temperature to afford [(q4- tBu2C2P2)2Co2(mu,q4:q4-P4) (8), which is a rare example of a tripledecker complex with a P42- middle deck. The electronic structures of 6-8 are analyzed using theoretical methods including an analysis of intrinsic bond orbitals and magnetic response theory. Thereby, the aromatic nature of P5- and SnP42- was confirmed, while for P42-, a specific type of symmetry-induced weak paramagnetism was found that is distinct from conventional antiaromatic species.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftJournal of the American Chemical Society
Verlag:AMER CHEMICAL SOC
Ort der Veröffentlichung:WASHINGTON
Band:144
Nummer des Zeitschriftenheftes oder des Kapitels:44
Seitenbereich:S. 20434-20441
Datum31 Oktober 2022
InstitutionenChemie und Pharmazie > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Robert Wolf
Chemie und Pharmazie > Institut für Organische Chemie > Arbeitskreis Prof. Dr. Ruth Gschwind
Identifikationsnummer
WertTyp
10.1021/jacs.2c08754DOI
Stichwörter / KeywordsCOORDINATION CHEMISTRY; MOLECULAR-STRUCTURE; GROUP-14 METALLOLES; ORGANIC-CHEMISTRY; COBALT COMPLEXES; X-RAY; CRYSTAL; PHOSPHORUS; OXIDE; DIMERIZATION;
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenJa
URN der UB Regensburgurn:nbn:de:bvb:355-epub-531556
Dokumenten-ID53155

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