Crystallographic and Theoretical Investigations of Er2@C2 n (2 n=82, 84, 86): Indication of Distance‐Dependent Metal–Metal Bonding Nature. Issue 49 (8th August 2019)

• Record Type: Journal Article
• Authors: Hu, Shuaifeng; Shen, Wangqiang; Yang, Le; Duan, Guangxiong; Jin, Peng; Xie, Yunpeng; Akasaka, Takeshi; Lu, Xing
• Is Part Of: Chemistry. Volume 25:Issue 49(2019)
• Page Start: 11538
• Page End: 11544
• Publication Date: 2019-08-08
• Subjects: cluster compounds -- density functional calculations -- endohedral metallofullerenes -- metal–metal bonds -- structure elucidation; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201902321
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Successful isolation and characterization of a series of Er‐based dimetallofullerenes present valuable insights into the realm of metal–metal bonding. These species are crystallographically identified as Er2 @ Cs (6)‐C82, Er2 @ C 3 v (8)‐C82, Er2 @ C 1 (12)‐C84, and Er2 @ C 2 v (9)‐C86, in which the structure of the C 1 (12)‐C84 cage is unambiguously characterized for the first time by single‐crystal X‐ray diffraction. Interestingly, natural bond orbital analysis demonstrates that the two Er atoms in Er2 @ Cs (6)‐C82, Er2 @ C 3 v (8)‐C82, and Er2 @ C 2 v (9)‐C86 form a two‐electron‐two‐center Er−Er bond. However, for Er2 @ C 1 (12)‐C84, with the longest Er⋅⋅⋅Er distance, a one‐electron‐two‐center Er−Er bond may exist. Thus, the difference in the Er⋅⋅⋅Er separation indicates distinct metal bonding natures, suggesting a distance‐dependent bonding behavior for the internal dimetallic cluster. Additionally, electrochemical studies suggest that Er2 @C82–86 are good electron donors instead of electron acceptors. Hence, this finding initiates a connection between metal–metal bonding chemistry and fullerene chemistry. Abstract : One‐electron bonds : An array of dierbium metallofullerenes has been unambiguously characterized as Er2 @ Cs (6)‐C82, Er2 @ C 3 v (8)‐C82, Er2 @ C 1 (12)‐C84, and Er2 @ C 2 v (9)‐C86 . Interestingly, density functional theory calculations unveil the two‐electron and one‐electron occupied Er−Er bonds for Er2 @C82, 86 and Er2 @C84, respectively, dependent on the Er⋅⋅⋅Er separations.