Complexes of Gold(I), Silver(I), and Copper(I) with Pentaaryl[60]fullerides

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• 作者：Merissa Halim ; Robert D. Kennedy ; Mitsuharu Suzuki ; Saeed I. Khan ; Paula L. Diaconescu ; Yves Rubin
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：May 4, 2011
• 年：2011
• 卷：133
• 期：17
• 页码：6841-6851
• 全文大小：1187K
• 年卷期：v.133,no.17(May 4, 2011)
• ISSN：1520-5126

文摘

Gold(I), silver(I), and copper(I) phosphine complexes of 6,9,12,15,18-pentaaryl[60]fullerides 1a and 1b, namely, [(4-MeC₆H₄)₅C₆₀]Au(PPh₃) (2a), [(4-t-BuC₆H₄)₅C₆₀]Au(PPh₃) (2b), [(4-MeC₆H₄)₅C₆₀]Ag(PCy₃) (3a), [(4-t-BuC₆H₄)₅C₆₀]Ag(PPh₃) (3b), [(4-t-BuC₆H₄)₅C₆₀]Ag(PCy₃) (3c), [(4-MeC₆H₄)₅C₆₀]Cu(PPh₃) (4a), and [(4-t-BuC₆H₄)₅C₆₀]Cu(PPh₃) (4b), have been synthesized and characterized spectroscopically. All complexes except for 3c were also characterized by single-crystal X-ray diffraction. Several coordination modes between the cyclopentadienyl ring embedded in the fullerene and the metal centers are observed, ranging from 畏¹ with a slight distortion toward 畏³ in the case of gold(I), to 畏²/畏³ for silver(I), and 畏⁵ for copper(I). Silver complexes 3a and 3b are rare examples of crystallographically characterized Ag(I) cyclopentadienyls whose preparation was possible thanks to the steric shielding provided by fullerides 1a and 1b, which stabilizes these complexes. Silver complexes 3a and 3b both display unexpected coordination of the cyclopentadienyl portion of the fulleride anion with Ag(I). DFT calculations on the model systems (H₅C₆₀)M(PH₃) and CpMPH₃ (M = Au, Ag, or Cu) were carried out to probe the geometries and electronic structures of these metal complexes.