Homoleptic Silver Complexes of the Cages P4Se3 and As4S3. Issue 11 (4th October 2018)

• Record Type: Journal Article
• Authors: Weis, Philippe; Hettich, Clarissa; Kratzert, Daniel; Krossing, Ingo
• Other Names: Gudat Dietrich guestEditor.; Orthaber Andreas guestEditor.; Slootweg J. Chris guestEditor.; Streubel Rainer guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 11/12(2019)
• Page Start: 1657
• Page End: 1668
• Publication Date: 2018-10-04
• Subjects: Coordination chemistry -- Silver -- Weakly coordinating anion (WCA) -- Mass spectrometry; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201800743
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : By reacting P4 Se3 and As4 S3 with Ag[Al(OR F )4 ] {–R F = –C(CF3 )3 or – hfip [= –C(H)(CF3 )2 ]} in suitable solvents, Ag(P4 Se3 )[Al(O hfip )4 ] (1 ), Ag(P4 Se3 )2 [Al(OR F )4 ] (2 ), Ag(P4 Se3 )3 [Al(OR F )4 ] (3 ), Ag2 (As4 S3 )3 [Al(OR F )4 ]2 (4 ) and Ag(As4 S3 )2 [Al(OR F )4 ] (5 ) were synthesized and characterized by SC‐XRD, Mass spectrometry, Raman spectroscopy as well as solution NMR spectroscopy. When using stronger coordinating anions, only P4 Se3 forms an isolable complex yielding 1 featuring a [Ag2 (P4 Se3 )2 ] 2+ core capped by anions acting as the first example of P4 Se3 coordinating through selenium atoms. Upon using the weakly coordinating anion [Al{OC(CF3 )3 }4 ] –, the dimeric complexes 2 and 4 are accessible in dichloromethane or ortho ‐difluorobenzene ( o ‐dfb), respectively. Complex 2 shows isolated [Ag2 (P4 Se3 )4 (CH2 Cl2 )2 ] 2+ dications with a [Ag2 (P4 Se3 )2 ] 2+ core similar to 1 . Complex 4 shows isolated [Ag2 (As4 S3 )3 ] 2+ dications featuring a weak argentophilic contact. All of these complexes include solvent molecules or anions in the coordination sphere of the metal. When switching to the polar yet non‐coordinating solvent SO2, the coordination spheres are filled with additional ligands and compounds 3 and 5 form. Complex 3 shows condensed [Ag(P4 Se3 )3 ] + units yielding a one dimensional chain and represents the first homoleptic metal(P4 Se3 ) complex. Complex 5 shows a similar paddle wheel structure as in 4 with interconnecting As4 S3 ligands and is the first known example of a homoleptic metal(As4 S3 ) complex. Abstract : To be or not to be coordinated, that is the question investigated by the study of the coordination behavior of the weakly basic cage molecules P4 Se3 and As4 S3 . Using suitable Ag[WCA] salts and the polar yet non‐coordinating solvent SO2 made it possible to characterize the homoleptic complexes of these ligands, whereas stronger coordinating anions or solvents such as CH2 Cl2 and ortho ‐difluorobenzene yield dimeric structures displaying new coordination modes.