caa a22 4500 605510806 CHVBK 20210128100647.0 cr unu---uuuuu 210128e20150101xx s 000 0 eng 10.1007/s00894-014-2546-4 doi (NATIONALLICENCE)springer-10.1007/s00894-014-2546-4 Binuclear cyclopentadienylrhenium hydride chemistry: terminal versus bridging hydride and cyclopentadienyl ligands [Elektronische Daten] [Xiaozhen Gao, Nan Li, R. King, Henry Schaefer III] Theoretical studies predict the lowest energy structures of the binuclear cyclopentadienylrhenium hydrides Cp2Re2H n (Cp = η5-C5H5; n = 4, 6, 8) to have a central doubly bridged Re2(μ-H)2 unit with terminal η5-Cp rings and the remaining hydrides as terminal ligands. However, the lowest energy Cp2Re2H2 structure by more than 12kcalmol−1 has one terminal η5-Cp ring, a bridging η3,η2-Cp ring, and two terminal hydride ligands bonded to the same Re atom. The lowest energy hydride-free Cp2Re2 structure is a perpendicular structure with two bridging η3,η2-Cp rings. The previously predicted bent singlet Cp2Re2 structure with terminal η5-Cp rings and a formal Re-Re sextuple bond lies ∼37kcalmol−1 above this lowest energy (η3,η2-Cp)2Re2 structure. The thermochemistry of the CpReH n and Cp2Re2H n systems is consistent with the reported synthesis of the permethylated derivatives Cp*ReH6 and Cp*2Re2H6 (Cp* = η5-Me5C5) as very stable compounds. Additionally, natural bond orbital analysis, atoms-in-molecules and overlap population density-of-state in AOMIX were applied to present the existence of rhenium-rhenium multiple bonds. Graphical Abstract The lowest energy Cp2Re2H n (Cp = η5-C5H5; n = 4, 6, 8) structures have a central doubly bridged Re2(μ-H)2 unit. However, the lowest Cp2Re2H2 structure by more than 12kcalmol−1 has one terminal η5-Cp ring, a bridging η3,η2-Cp ring, and two terminal hydride ligands bonded to the same Re atom. The lowest energy hydride-free Cp2Re2 structure is a perpendicular structure with two bridging η3,η2-Cp rings Springer-Verlag Berlin Heidelberg, 2015 Binuclear rhenium hydrides nationallicence Thermochemistry nationallicence Density functional theory nationallicence Gao Xiaozhen School of Mechatronical Engineering, Beijing Institute of Technology, 100081, Beijing, China aut Li Nan School of Mechatronical Engineering, Beijing Institute of Technology, 100081, Beijing, China aut King R. Department of Chemistry and Center for Computational Chemistry, University of Georgia, Cedar Street, 30602, Athens, Georgia, USA aut Schaefer III Henry Department of Chemistry and Center for Computational Chemistry, University of Georgia, Cedar Street, 30602, Athens, Georgia, USA aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/1(2015-01-01), 1-16 1610-2940 21:1<1 2015 21 894 https://doi.org/10.1007/s00894-014-2546-4 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-014-2546-4 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Gao Xiaozhen School of Mechatronical Engineering, Beijing Institute of Technology, 100081, Beijing, China aut NATIONALLICENCE 700 1- Li Nan School of Mechatronical Engineering, Beijing Institute of Technology, 100081, Beijing, China aut NATIONALLICENCE 700 1- King R. Department of Chemistry and Center for Computational Chemistry, University of Georgia, Cedar Street, 30602, Athens, Georgia, USA aut NATIONALLICENCE 700 1- Schaefer III Henry Department of Chemistry and Center for Computational Chemistry, University of Georgia, Cedar Street, 30602, Athens, Georgia, USA aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/1(2015-01-01), 1-16 1610-2940 21:1<1 2015 21 894