In:
Chemistry – A European Journal, Wiley, Vol. 23, No. 27 ( 2017-05-11), p. 6552-6561
Abstract:
Additions of adamantylidene (Ad) to M 3 N@ I h ‐C 80 (M=Sc, Lu) and Sc 3 N@ D 5 h ‐C 80 have been accomplished by photochemical reactions with 2‐adamantyl‐2,3′‐[3 H ]‐diazirine ( 1 ). In M 3 N@ I h ‐C 80 , the addition led to rupture of the [6,6]‐ or [5,6] ‐bonds of the I h ‐C 80 cage, forming the [6,6]‐open fulleroid as the major isomer and the [5,6] ‐open fulleroid as the minor isomer. In Sc 3 N@ D 5 h ‐C 80 , the addition also proceeded regioselectively to yield three major isomeric Ad mono‐adducts, despite the fact that there are nine types of C−C bonds in the D 5 h ‐C 80 cage. The molecular structures of the seven Ad mono‐adducts, including the positions of the encaged trimetallic nitride clusters, have been unambiguously determined through single‐crystal XRD analyses. Furthermore, results have shown that stepwise addition of Ad to Lu 3 N@ I h ‐C 80 affords several Ad bis‐adducts, two of which have been isolated and characterized. The X‐ray structure of one bis‐adduct clearly revealed that the second Ad addition took place at a [6,6]‐bond close to an endohedral metal atom. Theoretical calculations have also been performed to rationalize the regioselectivity.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201700049
Language:
English
Publisher:
Wiley
Publication Date:
2017
detail.hit.zdb_id:
1478547-X
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