ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Transition Metal Substituted Phosphanes, Arsanes, and Stibanes, XXIII. Stable Transition Metal Dimethylarsanes Bearing a Tricarbonyl(cyclopentadienyl)chromium, -molybdenum or -tungsten SubstituentBy the interaction of (CH3)2AsCl with [C5H5(CO)3M]Na or C5H5(CO)3M - Si(CH3)3 stable carbonyl(cyclopentadienyl)metal dimethylarsanes of the formula C5H5(CO)3M - As(CH3)2 (M = Cr, Mo, W) (1 - 3) are obtained for the first time. Their thermal treatment in the solid state yields [(CH3)2As]2 and [C5H5(CO)3M]2, in solution with loss of CO the cyclic species [C5H5(CO)2M - As(CH3)2]2 4a (Mo), 4b (W) are formed. Under photolytic conditions in addition to 4a, b the aggregation products trans-C5H5(CO)2[C5H5(CO)3M - As(CH3)2]M - As (CH3)2 (5a, b) and [trans-C5H5(CO)2M - As(CH3)2]x (6a, b) are isolated. Alkyl halides and (CH3)3SiI readily convert 1 - 3 into the cationic complexes [C5H5(CO)3M - As(CH3)2R]X (R = CH3, CH2C(O)C6H5, CH2Si(CH3)3, Si(CH3)3; X = Br, I) (7a - f). With chlorine or bromine the extremely labile dihalogen adducts C5H5(CO)3M - As(CH3)2Hal2 (8a - c) are formed, which rapidly decompose to (CH3)2AsHal and C5H5(CO)3MoHal or C5H5(CO)3WH. HCl, CF3CO2H, (CH3)3SnH, Na/Hg, CH3MgI, and (CH3)3PCH2 cleave the transition metal-arsenic bond under very mild conditions.
Notes:
Durch die Reaktion von (CH3)2AsCl mit [C5H5(CO)3M]Na oder C5H5(CO)3M - Si(CH3)3 werden erstmals stabile Carbonyl(cyclopentadienyl)metall-dimethylarsane der Form C5H5(CO)3M - As(CH3)2 (M = Cr, Mo, W) (1 - 3) erhalten. Ihre thermische Behandlung in Substanz liefert [(CH3)2As]2 und [C5H5(CO)3M]2, in Lösung unter CO-Eliminierung die cyclischen Verbindungen [C5H5(CO)2M - As(CH3)2]2 4a (Mo), 4b (W). Unter photolytischen Bedingungen werden zusätzlich zu 4a, b die Aggregationsprodukte trans-C5H5(CO)2[C5H5(CO)3M - As(CH3)2]M - As(CH3)2 (5a, b) und [trans-C5H5(CO)2M - As(CH3)2]x (6a, b) isoliert. Alkylhalogenide und (CH3)3SiI überführen 1 - 3 glatt in die kationischen Komplexe [C5H5(CO)3M - As(CH3)2R]X (R = CH3, CH2C(O)C6H5, CH2Si(CH3)3, Si(CH3)3; X = Br, I) (7a - f). Mit Chlor oder Brom werden die extrem labilen Dihalogenaddukte C5H5(CO)3M - As(CH3)2Hal2 (8a - c) gebildet, die rasch zu (CH3)2AsHal und C5H5(CO)3MoHal bzw. C5H5(CO)3WH zerfallen. HCl, CF3CO2H, (CH3)3SnH, Na/Hg, CH3MgI und (CH3)3PCH2 spalten die Übergangsmetall-Arsenbindung unter sehr milden Bedingungen.
Additional Material:
7 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19801131020
