New Adamantane-like Silicophosphate Cage and Its Reactivity toward Tris(pentafluorophenyl)borane
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 PO moieties and six O–SiPh2–O bridging groups. Compound 1...
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| Published in: | Inorganic chemistry Vol. 56; no. 17; pp. 10699 - 10705 |
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| Main Authors: | , , , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
United States
American Chemical Society
05-09-2017
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| Online Access: | Get full text |
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| Summary: | 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 PO moieties and six O–SiPh2–O bridging groups. Compound 1 was further reacted with the Lewis acid B(C6F5)3. We observed adduct formation by coordination through the PO→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 Ph12Si6O16P4·3B(C6F5)3 (2); the remaining PO 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 Si–O–P linkages in the adamantane cage during the reaction of 1 with 4 equiv of B(C6F5)3. The bis-adduct Ph6Si3O8P2·2B(C6F5)3 (3) was formed with an inorganic core representing half of the parent molecule 1. |
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| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 0020-1669 1520-510X |
| DOI: | 10.1021/acs.inorgchem.7b01572 |