%0 Journal Article %T B-H Functionalization of Hydrogen-Rich [(Cp*V)(2) (B2H6)(2)]: Synthesis and Structures of [(Cp*V)(2)(B2X2)(2)H-8] (X = CI, SePh; Cp* = eta(5)-C5Me5) %+ Indian Institute of Technology Madras (IIT Madras) %+ Institut des Sciences Chimiques de Rennes (ISCR) %A Haridas, Anagha %A Kar, Sourav %A Raghavendra, Beesam %A Roisnel, Thierry %A Dorcet, Vincent %A Ghosh, Sundargopal %Z Council of Scientific and Industrial Research, CSIR (Project No. 01(2939)/18/emr-ii), India %< avec comité de lecture %@ 0276-7333 %J Organometallics %I American Chemical Society %V 39 %N 1 %P 58-65 %8 2020-01-13 %D 2020 %R 10.1021/acs.organomet.9b00609 %Z Chemical SciencesJournal articles %X We have recently reported the perchlorinated diniobaborane species [(Cp*Nb)(2)(B2H4Cl2)(2)] from [(Cp*Nb)(2)(B2H6)(2)] using CCl4 as a chlorinating agent. In an attempt to isolate the vanadium analogue, we have isolated [(Cp*V)(2)(B2H6)(2)] (1) from the reaction of (Cp*VCl2)(3) with [LiBH4THF] followed by thermolysis with excess [BH3 center dot THF]. Subsequently, the thermolysis of 1 with CCl4 for a prolonged period of time afforded the perchlorinated divanadaborane [(Cp*V)(2)(B2H4Cl2)(2)] (2) along with the formation of the bichlorinated divanadaborane [(Cp*V)(2)(B2H5Cl)(2)] (3) and trichlorinated divanadaborane [(Cp*V)(2)(B2H4Cl2)(B2H5Cl)] (4). Similarly, in order to functionalize the terminal B-H by a {SePh} group, thermolysis of 1 was carried out with Ph2Se2, which yielded the persubstituted divanadaborane [(Cp*V)(2) {B2H4(SePh)(2)}(2)] (5) in parallel to the formation of [(Cp*V)(2) {B4H11(SePh)}] (6). Compound 5 is very fascinating in that all of the terminal B-H hydrogens of 1 have been substituted by {SePh} ligands. All of the compounds have been characterized by H-1, B-11, and C-13 NMR spectroscopy, mass spectrometry, IR spectroscopy, and single-crystal X-ray analysis. Density functional theory (DFT) and TD-DFT calculations provided a further understanding regarding the electronic structures, bonding, and electronic transitions of these persubstituted vanadaborane species. %G English %2 https://univ-rennes.hal.science/hal-02470143/document %2 https://univ-rennes.hal.science/hal-02470143/file/Ghosh_et%20al_2020_BH%20Functionalization%20of%20Hydrogen-Rich_accepted.pdf %L hal-02470143 %U https://univ-rennes.hal.science/hal-02470143 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR-CD %~ STATS-UR1 %~ UR1-SPM %~ ISCR-PRATS %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ TEST-HALCNRS %~ UR1-MMS %~ TEST2-HALCNRS