Synthesis and structural characterization of some 1:1 adducts of silver(I) salts with (hindered) PR3 bases (R = phenyl, o-tolyl, cyclohexyl)

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Effendy, Corrado Di Nicola, Peter C. Healy, Fabio Marchetti, Claudio Pettinari, Brian W. Skelton, Alessia Tombesi, Allan H. White

2022 Inorganica Chimica Acta Vol. 536 Article Cited by 0 Quartile

Abstract

Syntheses, spectroscopy and single crystal X-ray structural characterizations are recorded for a number of adducts AgX: PR3 (1:1)n obtained from the reaction of silver(I) salts with sterically hindered tertiary phosphine bases, extending previous studies. With tris(o-tolyl)phosphine, P(o-tolyl)3, binuclear adducts AgX: P(o-tolyl)3 (1:1)2 are defined, in arrays with eight-membered central rings [(o-to1yl)3PAg(μ-tfa)2AgP(o-tolyl)3] (1) (tfa = trifluoroacetate, O.CO.CF3) where two independent atoms of the anion bridge to the two silver atoms, and four-membered central rings where one atom bridges (Cl, NCO, acetate (= 'ac', O.CO.CH3)) (complexes 2–4); the perchlorate (5) is intermediate, one perchlorate bridging via one oxygen and the other by two. The nitrate is mononuclear, [(o-tolyl)3PAgO2NO], (6) with chelating nitrate. The bromide takes a tetranuclear 'cubane' form (7). With the cyanide, an interesting 2:1 AgCN: (o-tolyl)3P adduct (8) is defined as a two-dimensional polymer. The archetypical cubane series with triphenylphosphine is extended with a new bromide structure, MeCN solvated [(Ph3P)AgBr]4.0.22MeCN (9), to encompass also the cyanate [(Ph3P)Ag(NCO)]4 (10), isomorphous with the previously defined Cu/As/I chloroform solvate. The 'cubane' form is defined also for a further iodide polymorph AgI: Pcy3 (1:1)4 (11). © 2022

Affiliations

Chemistry, School of Molecular Sciences, University of Western Australia, M310, 35 Stirling Highway, Perth, 6009, WA, Australia; Jurusan Pendidikan Kimia, FMIPA Universitas Negeri Malang, Alan Surabaya 6, Malang, 65145, Indonesia; School of Science and Technologies, University of Camerino, via S. Agostino 1, MC, Camerino, 62032, Italy; Division of Science and Technology, Griffith University, Nathan, 4111, QLD, Australia; School of Pharmacy, University of Camerino, via S. Agostino 1, MC, Camerino, 62032, Italy