Publication details

New Adamantane-like Silicophosphate Cage and Its Reactivity toward Tris(pentafluorophenyl)borane

Authors

STÝSKALÍK Aleš BABIAK Michal MACHÁČ Petr RELICHOVÁ Bohuslava PINKAS Jiří

Year of publication 2017
Type Article in Periodical
Magazine / Source Inorganic Chemistry
MU Faculty or unit

Faculty of Science

Citation
Doi http://dx.doi.org/10.1021/acs.inorgchem.7b01572
Field Inorganic chemistry
Keywords silicophosphate; boranes; enantiomers; adamantane; conglomerate of homochiral crystals
Description The condensation reaction between Ph2Si(OC-(O)CH3)(2) and OP(OSiMe3)(3) leads to elimination of CH3C(O)OSiMe3 and the formation of the new silicophosphate cage molecule Ph12Si6P4O16 (1) with an adamantane-like core possessing four terminal P=O moieties and six OSiPh2O bridging groups. Compound 1 was further reacted with the Lewis acid B(C6F5)3. We observed adduct formation by coordination through the P=O -> B bonds and isolated and structurally characterized two new molecules. In the first of them, the adamantane-like cage is preserved and three phosphoryl oxygen atoms coordinate to boranes, forming Ph12Si6O16P4 center dot 3B(C6F5)(3) (2); the remaining P=O group is inverted toward the cage center pointing along a C-3 molecular axis. The molecule is chiral, and the compound 2 crystallizes as a conglomerate of homochiral crystals. Enantiomers 2M and 2P were both structurally characterized. The second adduct resulted from an unexpected reorganization of the SiOP linkages in the adamantane cage during the reaction of 1 with 4 equiv of B(C6F5)(3). The bis-adduct Ph6Si3O8P2 center dot 2B(C6F5)(3) (3) was formed with an inorganic core representing half of the parent molecule 1.
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