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Valence Electron Dependent Contraction of P6 Ring in [(CpM)2(μ,η6:η6-P6)] (M ═ V, Mo): A DFT Study
Gaurav Joshi1, Sreerag N Moorkkannur2, Eluvathingal D Jemmis1
1Inorganic and Physical Chemistry Department, Indian Institute of Science, Bangalore, 560012, India.
None:
The P6 ring in [(Cp*Mo)2(μ,η6:η6-P6)] contracts to the P5 complex [(Cp*Mo)2(μ,η5:η5-P5)][(MeNHC)2P] by MeNHC. In contrast, P6 ring in [(Cp*V)2(μ,η6:η6-P6)] contracts to P5 and P4 complexes [(Cp*V)2(μ,η5:η5-P5)][(MeNHC)2P] and [(Cp*V)2(μ,η4:η4-P4 MeNHC)]. In addition, an anionic form of the precursor [(Cp*V)2(μ,η6:η6-P6)][(MeNHC)2P] is also produced here. Mechanistic investigation using TPSSh-d4/Def2-TZVP method shows the importance of different spin states in the reaction and a possible outer sphere electron transfer aiding the ring contraction of P5 to P4. Valence electron count (VEC) determines the variety of spin states accessible to the complexes and plays a decisive role in deciding the fate of the middle deck.
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