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Cage‐Structured Triplatinacyclophanes
Author(s) -
Lindner Ekkehard,
Hermann Christian,
Baum Gerhard,
Fenske Dieter
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199904)1999:4<679::aid-ejic679>3.0.co;2-a
Subject(s) - chemistry , mesitylene , tris , trifluoromethanesulfonate , cationic polymerization , acetonitrile , rhenium , benzene , pyridine , medicinal chemistry , polymer chemistry , inorganic chemistry , organic chemistry , catalysis , biochemistry
The synthesis of the tris(triflate) 4 (Scheme 1) has been achieved by means of a straightforward three‐step reaction sequence. After initial lithiation of mesitylene, treatment of the obtained trilithium compound C 6 H 3 (CH 2 Li) 3 ( 2 ) with oxirane results in the formation of 1,3,5‐tris(3‐hydroxypropyl)benzene ( 3 ), which is then transformed to 4 by reaction with (CF 3 SO 2 ) 2 O in the presence of pyridine. Whereas 4 reacts with Na 2 [Os(CO) 4 ] in a somewhat complicated manner, similar reactions with Na[Re(CO) 5 ] and LiPPh 2 give the hydrocarbon‐bridged tris(rhenium) complex C 6 H 3 [(CH 2 ) 3 Re(CO) 5 ] 3 ( 5 ) and the tris(phosphane) C 6 H 3 [(CH 2 ) 3 PPh 2 ] 3 ( 6 ), respectively. Employing the high‐dilution method, from 6 and Cl 2 Pt(NCPh) 2 the nanoscaled tri‐ and hexaplatinacyclophanes 7 and 9 are available. Owing to the optimal geometry and flexibility of the cage in 7 , 1,2‐dichloroethane can be reversibly encapsulated. The molecular structure of 7 · 7 1,2‐Cl 2 C 2 H 4 was determined by an X‐ray structure analysis. The utility of the reactive metal centers in 7 has been demonstrated by replacing the chloro ligands by acetonitrile to give the cationic platinacyclophane 8 , in which, according to NMR studies, the cage‐like structure is preserved.