ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Transition Metal Carbyne Complexes, XXXVI. Nucleophilic Substitution on trans-Tetracarbonyl(organylcarbyne)(tetrafluoroborato) Complexes of Chromium and Tungsten with Triphenylphosphine, Cyanide and ThiocyanatePentacarbonyl[methoxy(phenyl)carbene]- and -[methoxy(methyl)carbene]tungsten(0) (1a, b) react in boron trifluoride dimethyletherate in the presence of a large excess of BF3 to form trans- (BF4)(CO)4WCR complexes (2a, b). In these two tungsten complexes 2a, b as well as in the analogous chromium complex mer-(BF4)(CO)3[P(CH3)3]CrCCH3 (4) the BF4 ligand is displaced easily by nucleophilic reagents. With thiocyanate, cyanide, and triphenylphosphine the corresponding neutral trans-isothiocyanato (6a, b) and trans-cyano complexes (7) as well as the cationic trans-(organylcarbyne)(triphenylphosphine)metal complexes (3, 5) are obtained similarly at low temperatures.
Notes:
Pentacarbonyl[methoxy(phenyl)carben]- und -[methoxy(methyl)carben]wolfram(0) (1a, b) reagieren in Bortrifluorid-dimethyletherat in Gegenwart eines großen Überschusses an BF3 zu trans- (BF4) (CO)4WCR-Komplexen (2a, b). Der am Metallatom koordinierte BF4-Ligand in den beiden Wolframkomplexen 2a, b sowie bei dem analogen Chromkomplex mer-(BF4)(CO)3-[P(CH3)3]CrCCH3 (4) kann durch nucleophile Reagentien leicht verdrängt werden. So lassen sich mit Rhodanid und Cyanid sowie Triphenylphosphin bei tiefen Temperaturen die entsprechenden neutralen trans-Isothiocyanato- (6a, b) und trans-Cyano-Komplexe (7) sowie die kationischen trans-(Organylcarbin)triphenylphosphin)metall-Komplexe (3, 5) erhalten.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19781110804
Permalink
