ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Complex Chemistry of Reactive Organic Compounds, XIV. The Reactions of Aliphatic Diazo Compounds with the Tricarbonyl(cyclopentadienyl) Hydrides of Molybdenum and TungstenDepending on their constitution, aliphatic diazo compounds 3 behave differently in their reactions with tricarbonyl(cyclopentadienyl)hydridomolybdenum (1) and -tungsten (2). Diazomethane (3a), diazoethane (3b), and 2-diazopropane (3c) are stabilized as alkane diazo ligands in complexes of the type C5H5M(CO)2[N2CHR1R2] (M = Mo: 6; M = W: 7). Phenyl-, (4-nitrophenyl)-, (4-methoxyphenyl)diazomethane (3d, e, f), and 9-diazofluorene (3g) form in clean reactions the carbene insertion products C5H5M(CO)3CHR1R2 (M = Mo: 4; M = W: 5), whereas ω-diazoacetophenone (3h) and diazodimedone (3i) yield the binuclear diazo complexes C5H5M(CO)3-M(CO)2C5H5[N2 = CR1R2] (M = Mo: 9; M = W: 10). Diethyl diazomalonate (3h) is coordinated as an imino-amido ligand in the coordination compound 14 which arises from a 1,1-insertion of 3k into the polar tungsten-hydrogen bond of 2.
Notes:
In ihrer Reaktivität gegenüber Tricarbonyl(cyclopentadienyl)hydridomolybdän (1) und -wolfram (2) weisen Diazoalkane 3 starke konstitutionsbedingte Unterschiede auf: Diazomethan (3a), Diazoethan (3b) und 2-Diazopropan (3c) werden als Alkandiazo-Liganden in Komplexen vom Typ C5H5M(CO)2[N2CHR1R2] (M = Mo: 6; M = W: 7) stabilisiert; Phenyl-, (4-Nitrophenyl)-, (4-Methoxyphenyl)diazomethan (3d, e, f) sowie 9-Diazofluoren (3g) bilden in glatten Reaktionen die Carben-Insertionsprodukte C5H5M(CO)3CHR1R2 (M = Mo: 4; M = W: 5), während ω-Diazoacetophenon (3h) wie auch Diazodimedon (3i) die zweikernigen Diazoketon-Komplexe C5H5M(CO)3-M(CO)2C5H5[N2 = CR1R2] (M = Mo: 9; M = W: 10) ergeben. Diazomalonsäure-diethylester (3k) wird im Zuge einer zur Koordinationsverbindung 14 führenden 1,1-Insertion in die polare Wolfram-Wasserstoff-Bindung von 2 als Imino-amido-Ligand komplexiert.
Additional Material:
8 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19771100310
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