ISSN:
0009-2940
Keywords:
Rhenium complexes
;
alcohols as ligands
;
Chiral alcohol complexes
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Reactions of dichloromethane complex [(η5-C5H5)Re(NO)-(PPh3)(ClCH2Cl)]⊕ BF4⊖ (2⊕ BF4⊖ and alcohols ROH give the title compounds [(η5-C5H5)Re(NO)-(PPh3)(ROH)]⊕ BF4⊖; (3⊕ BF4⊖; a: R = Me, b: Et, c: CH2Ph, d: t-Bu) in 91-95% yields as air-stable powders after workup. Reactions of 3a-c⊕ BF4⊖ and Et3N produce alkoxide complexes (η5-C5H5)Re(NO)-(PPh3)(OR) (4a-c, 80-90%), which in turn react with HBF4- OEt2 to give 3a-c⊕ BF4⊖. Reactions of 3a-c⊕ BF4⊖ and Ph3PX⊕ Br⊖ give the bromide complex (η5-C5H5)Re(NO)-(PPh3)(Br) (85-98%) and alcohols ROH. 3b,c⊕ BF4⊖ and aldehydes react to give π complexes [(η5-C5H5)Re(NO)(PPh3)(η2-O=CHR′)]⊕ BF4⊖ (〉94%). Reaction of 3b⊕ BF4⊖ and HSi(OEt)3 generates the hydride complex (η5-C5H5)Re(O)(PPh3)(H) (5, 77%). Reaction of 5 with Ph3C⊕ PF6⊖ and then ROH gives 3⊕ PF6⊖ (88-91%). NMR experiments establish the order O=CHR 〉 ROH 〉 ROR for ligand binding energies to the rhenium fragment [(η5-C5H5)Re(NO)(PPh3)]⊕.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19901230612
