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Poorters L, Armspach D, Matt D, Toupet L: alpha-TEPHOS: a cyclodextrin-derived tetraphosphine for multiple metal binding. Dalton Trans. 2007 Aug 7;(29):3195-202. Epub 2007 May 24. The tetraphosphine 6 (A),6 (B),6 (D),6 (E)-tetradeoxy-6 (A),6 (B),6 (D),6 (E)-tetra (diphenylphosphiny l)-2 (A),2 (B),2 (C),2 (D),2 (E),2 (F),3 (A),3 (B),3 (C),3 (D),3 (E),3 (F),6 (C),6 (F)-t etradeca-O-methyl-alpha-cyclodextrin (alpha-TEPHOS) has been prepared in high yield by reacting 6 (A),6 (B),6 (D),6 (E)-tetra-O-methylsulfonyl-2 (A),2 (B),2 (C),2 (D), 2 (E),2 (F),3 (A),3 (B),3 (C),3 (D),3 (E),3 (F),6 (C),6 (F)-tetradeca-O-methyl-alpha -cyclodextrin with excess PPh (2) Li. The product was purified in its BH (3)-protected form. alpha-TEPHOS is the first optically active tetraphosphine in which the four phosphine units are tethered to a cavity-shaped scaffold. When reacted with [AuCl (tetrahydrothiophene)], alpha-TEPHOS led to the corresponding tetragold complex [(alpha-TEPHOS)(AuCl)(4)] in which the four gold atoms are all located close to the primary face of the cyclodextrin. Reaction with [PdCl (o-C (6) H (4) CH (2) NMe (2))](2) gave the C (2)-symmetrical complex [(alpha-TEPHOS){PdCl (o-C (6) H (4) CH (2) NMe (2))}(4)]. Treatment of the ligand with two equiv. of [Rh (norbornadiene)(tetrahydrofuran)(2)] BF (4) afforded selectively the bimetallic complex [(alpha-TEPHOS){Rh (norbornadiene)}(2)](BF (4))(2) in which each metal centre is coordinated to two phosphorus atoms belonging to adjacent glucose units. |
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