Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
J Am Chem Soc. 2011 May 4;133(17):6841-51. doi: 10.1021/ja201297r. Epub 2011 Apr 8.
Gold(I), silver(I), and copper(I) phosphine complexes of 6,9,12,15,18-pentaaryl[60]fullerides 1a and 1b, namely, [(4-MeC(6)H(4))(5)C(60)]Au(PPh(3)) (2a), [(4-t-BuC(6)H(4))(5)C(60)]Au(PPh(3)) (2b), [(4-MeC(6)H(4))(5)C(60)]Ag(PCy(3)) (3a), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PPh(3)) (3b), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PCy(3)) (3c), [(4-MeC(6)H(4))(5)C(60)]Cu(PPh(3)) (4a), and [(4-t-BuC(6)H(4))(5)C(60)]Cu(PPh(3)) (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 η(1) with a slight distortion toward η(3) in the case of gold(I), to η(2)/η(3) for silver(I), and η(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 (H(5)C(60))M(PH(3)) and CpMPH(3) (M = Au, Ag, or Cu) were carried out to probe the geometries and electronic structures of these metal complexes.
6,9,12,15,18-五芳基[60]富勒烯 1a 和 1b 的金(I)、银(I)和铜(I)膦配合物，即 [(4-MeC(6)H(4))(5)C(60)]Au(PPh(3)) (2a)、[(4-t-BuC(6)H(4))(5)C(60)]Au(PPh(3)) (2b)、[(4-MeC(6)H(4))(5)C(60)]Ag(PCy(3)) (3a)、[(4-t-BuC(6)H(4))(5)C(60)]Ag(PPh(3)) (3b)、[(4-t-BuC(6)H(4))(5)C(60)]Ag(PCy(3)) (3c)、[(4-MeC(6)H(4))(5)C(60)]Cu(PPh(3)) (4a) 和 [(4-t-BuC(6)H(4))(5)C(60)]Cu(PPh(3)) (4b)，已被合成并通过光谱学进行了表征。除了 3c 之外，所有配合物都通过单晶 X 射线衍射进行了表征。观察到嵌入富勒烯的环戊二烯基与金属中心之间的几种配位模式，从金(I)的轻微扭曲的 η(1)到银(I)的 η(2)/η(3)，以及铜(I)的 η(5)。银配合物 3a 和 3b 是晶体化学表征的 Ag(I)环戊二烯基的罕见实例，其制备之所以成为可能，是因为 1a 和 1b 富勒烯提供了空间位阻，稳定了这些配合物。银配合物 3a 和 3b 都显示出富勒烯阴离子的环戊二烯部分与 Ag(I)的意想不到的配位。对模型体系 (H(5)C(60))M(PH(3)) 和 CpMPH(3) (M = Au、Ag 或 Cu) 的 DFT 计算用于探测这些金属配合物的几何形状和电子结构。
