Premium
Mono‐ and Dinuclear Rhenium Polyhydride Complexes Bearing the Chelating Ligand 1,2‐Bis(dicyclohexylphosphanyloxy)ethane
Author(s) -
Bolaño Sandra,
Bravo Jorge,
GarcíaFontán Soledad
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.200400405
Subject(s) - chemistry , rhenium , protonation , hydride , ligand (biochemistry) , crystallography , chelation , alkoxy group , stereochemistry , medicinal chemistry , decomposition , metal , inorganic chemistry , organic chemistry , ion , biochemistry , alkyl , receptor
Variable‐temperature NMR spectroscopic studies of new rhenium polyhydride compounds of the type [ReH 7 (dcype)] ( 1 ), [Re 2 H 8 (dcype) 2 ] ( 3 ) and [ReH 5 (dcype)L] ( 5a − f ) [dcype = Cy 2 PO(CH 2 ) 2 OPCy 2 ; L = PPh n (OR) 3− n , n = 0−2, R = Me, Et] show them to be highly fluxional classical hydride complexes. In the case of the ethoxy compounds 5b , 5d and 5f , three hydride interchange processes were observed in the temperature range 283−173 K and their activation parameters were determined by NMR line‐shape analysis. A mechanism is proposed for each. Protonation of 1 and 5 with HBF 4 ·OMe 2 gave the nonclassical hydrides [ReH 8 (dcype)]BF 4 ( 2 ) and [ReH 6 (dcype)L]BF 4 ( 6 ) which are relatively stable. Compound 2 decomposes at 273 K in solution releasing H 2 ,whereas compound 6 can be stored at room temperature for more than 24 h without decomposition. Protonation of 3 with HBF 4 ·OMe 2 gave the classical dinuclear hydride [Re 2 H 9 (dcype) 2 ]BF 4 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)