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Selective Reaction of Aminorhenium Complexes and the Formation of Cp‐N‐P Tridentate Complexes
Author(s) -
Wang TeinFu,
Wang TanChing,
Wen YuhSheng
Publication year - 2004
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/ejic.200300650
Subject(s) - chemistry , ligand (biochemistry) , nucleophile , medicinal chemistry , cyclopentadienyl complex , rhenium , cationic polymerization , denticity , intramolecular force , stereochemistry , metal , polymer chemistry , organic chemistry , catalysis , receptor , biochemistry
Rhenium complexes containing cyclopentadienyl‐amino‐phosphanyl tridentate ligands have been prepared starting from a cyclopentadienyl‐amino bidentate complex in a controlled manner. Dehydrobromination of [η 5 :η 1 ‐C 5 H 4 CH 2 CH 2 NH(CH 3 )Re(CO) 2 Br] + ( 2 ) was carried out selectively at low temperature to give an exocyclic iminorhenium complex [η 5 :η 1 ‐C 5 H 4 CH 2 CH 2 N(=CH 2 )Re(CO) 2 ] ( 5 ). Selective N ‐methylation provided a cationic heterocyclopropane complex 8 which reacted with various nucleophiles ( t BuNH 2 , NaOCH 3 , KPPh 2 ) to give precursors for tridentate complexes. A formal oxidation of the carbonyl ligand to a labile carbon dioxide ligand was accomplished by oxidation with peroxy acid. Intramolecular N ligand displacement furnished the Cp‐N‐P tridentate complex. The relative stability of the N, P and CO ligands was revealed when an η 3 ‐allyl ligand was formed. The N ligand became detached from the metal rather than the P or CO ligands as the η 1 ‐allyl was transformed to the corresponding η 3 ‐allyl coordination mode. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)