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Binuclear cyclopentadienylrhenium hydride chemistry: terminal versus bridging hydride and cyclopentadienyl ligands

  • Xiaozhen Gao
  • Nan Li
  • R. Bruce King
  • Henry F. SchaeferIII
Original Paper

Abstract

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 12 kcal mol−1 has one terminal η5-Cp ring, a bridging η32–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 η32–Cp rings. The previously predicted bent singlet Cp2Re2 structure with terminal η5-Cp rings and a formal Re–Re sextuple bond lies ∼37 kcal mol−1 above this lowest energy (η32–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 12 kcal mol−1 has one terminal η5–Cp ring, a bridging η32–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 η32–Cp rings

Keywords

Binuclear rhenium hydrides Thermochemistry Density functional theory 

Notes

Acknowledgments

We are indebted to the Excellent Young Scholars Research Fund of Beijing Institute of Technology (2012YG0202 and 2014CX04024), Beijing Natural Science Foundation (2132033, and 2132035), Beijing Higher Education Young Elite Teacher Project(YETP1177) and the National Natural Science Foundation of China (61440020) and the U.S. National Science Foundation (Grants CHE-1057466 and CHE-1054286) for support of this research.

Supplementary material

894_2014_2546_MOESM1_ESM.pdf (334 kb)
ESM 1 (PDF 334 kb)

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Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  1. 1.School of Mechatronical EngineeringBeijing Institute of TechnologyBeijingChina
  2. 2.Department of Chemistry and Center for Computational ChemistryUniversity of GeorgiaAthensUSA
  3. 3.State Key Laboratory of Explosion Science and TechnologyBeijing Institute of TechnologyBeijingPeople’s Republic of China

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