Theoretically predicted ferrocene analogues with triplet aromatic CB5H5 ligands

• Published in: Journal of molecular modeling 2017-11, Vol.23 (11), p.1-7, Article 325
• Main Authors: Zhang, Shuqing, Duan, Yuhan, Cong, Mingyu, Zhao, Ruiqi, Chai, Haoyu, Guo, Jiayi, Ding, Shan, Hou, Jianhua
• Format: Article
• Language: English
• Subjects: Boron; Characterization and Evaluation of Materials; Charge distribution; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Ligands; Molecular Medicine; Original Paper; Predictions; Theoretical and Computational Chemistry
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-017-3498-2

Three ferrocene analogues, D 5h (η 5 -CB 5 H 5 ) 2 M (M = Fe 2− , Co − , and Ni), with triplet aromatic CB 5 H 5 ligands have been predicted at TPSSh/6–311+G(d,p) level. We find that the M atom interacts drastically with the two CB 5 H 5 ligands through a nearly fully-filled 3d subshell, which is different from (η 5 -C 5 H 5 ) 2 Fe. The natural population analyses suggest that (η 5 -CB 5 H 5 ) 2 M have an unconventional charge distribution, i.e., the M atom is negatively charged, while the two boron rings are positively charged. The analyses of the electronic and dynamic stabilities indicate that (η 5 -CB 5 H 5 ) 2 Co − is the most stable among (η 5 -CB 5 H 5 ) 2 M. Thus, we theoretically confirm that the triplet aromatic CB 5 H 5 cluster can be regarded as a potential new ligand. Our theoretical predictions are awaiting future experimental verification.