Activation of molecular hydrogen over a binuclear complex with Rh2S2 core: DFT calculations and NMR mechanistic studies

Journal of the American Chemical Society
Andrea IencoCarlo Mealli

Abstract

The dicationic complex [(triphos)Rh(mu-S)(2)Rh(triphos)](2+), 1 (modeled as 1c) [triphos = CH(3)C(CH(2)PPh(2))(3)], is known to activate two dihydrogen molecules and produce the bis(mu-hydrosulfido) product [(triphos)(H)Rh(mu-SH)(2)Rh(H)(triphos)](2+), 2 (modeled as 2b), from which 1 is reversibly obtained. The possible steps of the process have been investigated with DFT calculations. It has been found that each d(6) metal ion in 1c, with local square pyramidal geometry, is able to anchor one H(2) molecule in the side-on coordination. The step is followed by heterolytic splitting of the H-H bond over one adjacent and polarized Rh-S linkage. The process may be completed before the second H(2) molecule is added. Alternatively, both H(2) molecules are trapped by the Rh(2)S(2) core before being split in two distinct steps. Since the ambiguity could not be solved by calculations, (31)P and (1)H NMR experiments, including para-hydrogen techniques, have been performed to identify the actual pathway. In no case is there experimental evidence for any Rh-(eta(2)-H(2)) adduct, probably due to its very short lifetime. Conversely, (1)H NMR analysis of the hydride region indicates only one reaction intermediate which corresponds to the mono...Continue Reading

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Citations

Mar 18, 2009·Journal of the American Chemical Society·Koji IshiwataTakao Ikariya
Mar 13, 2010·Journal of the American Chemical Society·Piero MastrorilliSilvano Ellena
Mar 18, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Marco CiclosiMercedes Sanaú
Jun 9, 2009·Chemical Communications : Chem Comm·Seiji Ogo
Feb 18, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Chunbai ZhengSeiji Ogo
Apr 15, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Lili ZhaoZhi-Xiang Wang
Mar 12, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Hidetake SeinoYasushi Mizobe
Mar 12, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Shigeki Kuwata, Takao Ikariya
Apr 14, 2017·Accounts of Chemical Research·Lukas OmannMartin Oestreich
Oct 5, 2017·Chemistry : a European Journal·Felix KochHartmut Schubert
Oct 30, 2007·Angewandte Chemie·Carlo Mealli, Thomas B Rauchfuss
Feb 1, 2008·Angewandte Chemie·Hansjörg Grützmacher
Nov 15, 2008·Chemistry, an Asian Journal·Anne PoduskaCarlo Mealli
Mar 15, 2006·Chemistry : a European Journal·Marta MartínLuis A Oro
Apr 7, 2006·Chemistry : a European Journal·Andrew D PhillipsCarlo Mealli
Oct 6, 2015·Angewandte Chemie·Julia R Khusnutdinova, David Milstein
Jan 12, 2010·Chemical Communications : Chem Comm·Elzbieta StepowskaDatong Song
Jan 13, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Jingcong Tao, Shuhua Li
Aug 18, 2018·Journal of the American Chemical Society·Xin YuWenguang Wang
Aug 9, 2017·Inorganic Chemistry·Frank OlechnowiczRichard F Jordan

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