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The electronic structures of the PF5 complexes have been explored by DFT calculations. The DFT optimized geometries for [PF5(PMe3)], [PF5(PPh3)], and [PF4o-C6H4(PMe2)2]+ are in good agreement with their respective crystal structure geometries. DFT calculations on the PF5-L complexes reveal the P-L bond strength falls with L in the order PMe3 PPh3 AsMe3, consistent with the experimentally observed stabilities, and in the PF5-L complexes, electron transfer from L to PF5 on forming these complexes also follows the order PMe3
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