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Exploration of Bis(nickelation) of 1,1′-Bis(o-carborane)
| Content Provider | MDPI |
|---|---|
| Author | Mandal, Dipendu Rosair, Georgina M. |
| Copyright Year | 2020 |
| Description | The metalation of [Tl]2[1-(1′-3′,1′,2′-closo-TlC2B9H10)-3,1,2-closo-TlC2B9H10], with the smaller {Ni(dmpe)} fragment sourced from [Ni(dmpe)Cl2], is explored. The bis(metalated) products are obtained as a diastereoisomeric mixture. These isomers were separated, fully characterised spectroscopically and crystallographically and identified as rac-[1-(1′-3′-(dmpe)-3′,1′,2′-closo-NiC2B9H10)-3-(dmpe)-3,1,2-closo-NiC2B9H10] (1) and meso-[1-(1′-3′-(dmpe)-3′,1′,2′-closo-NiC2B9H10)-3-(dmpe)-3,1,2-closo-NiC2B9H10] (2). Previously, these 3,1,2-NiC2B9-3′,1′,2′-NiC2B9 architectures (where both cages are not isomerised), were inaccessible, and thus new structures can be achieved during bis(nickelation) with {Ni(dmpe)}. Further, the metalation of the tetra-thallium salt with the bulky {Ni(dppe)} fragment sourced from [Ni(dppe)Cl2] was also studied. These bis(nickelated) products were also fully characterised and are afforded as the stereospecific species rac-[1-(1′-3′-(dppe)-3′,1′,2′-closo-NiC2B9H10)-3-(dppe)-3,1,2-closo-NiC2B9H10] (3) and [1-(2′-4′-(dppe)-4′,1′,2′-closo-NiC2B9H10)-3-(dppe)-3,1,2-closo-NiC2B9H10] (4α). In the latter metalation, compound 3 shows intramolecular dihydrogen bonding, contributing to the stereospecificity, whereas isomerisation from 3,1,2 to 4,1,2- in the 4α is related to steric relief. |
| Starting Page | 16 |
| e-ISSN | 20734352 |
| DOI | 10.3390/cryst11010016 |
| Journal | Crystals |
| Issue Number | 1 |
| Volume Number | 11 |
| Language | English |
| Publisher | MDPI |
| Publisher Date | 2020-12-27 |
| Access Restriction | Open |
| Subject Keyword | Crystals Inorganic Chemistry 1,1′-bis(o-carborane) Deboronation Metalation Bis(nickelation) Diastereoisomers Stereospecific |
| Content Type | Text |
| Resource Type | Article |
