Syntheses of Cationic and Zwitterionic Cyclobutadiene Compounds of Cobalt(I). Crystal and Molecular Structure of Tricarbonyl(.eta.-1-methoxy-3-methyl-2-phenylcyclobutadiene)cobalt(1+) Hexafluorophosphate
Document Type
Article
Language
eng
Publication Date
1982
Publisher
American Chemical Society
Source Publication
Organometallics
Source ISSN
0276-7333
Abstract
The (r;3-cyclobutenonyl)cobalt complexes 1 react with trialkyloxonium salts to yield cationic cyclobutadiene compounds 2, which have been characterized by IR, XH NMR, and 13C NMR spectroscopy. Compounds 1 also react with BF3-OEt2 to afford the zwitterionic cyclobutadiene derivatives 4. Reactions of lb with PhCO+SbFe- or (CF3S02)20 produce 6 and 7, respectively. The CO ligands in 2a are displaced in refluxing benzene, affording the cationic sandwich complex 8, and the unstable zwitterion 4g can be trapped in refluxing benzene to give the zwitterionic sandwich complex 9. An X-ray crystallography investigation of 2i at -100 °C revealed a monoclinic crystal with space group P27/c (No. 14): a = 14.689 (5) A, b = 8.444 (2) A, c = 14.865 (5) A, (8 = 109.32 (3)°, Z = 4, R = 0.087, R„ = 0.051. The cyclobutadiene ring is planar, and substituent atoms bound to the ring are displaced away from the metal. The carbon-carbon distances within the cyclobutadiene ring are unequal, as are the cobalt-carbon distances.
Recommended Citation
Donaldson, William; Hughes, Russell P.; Davis, Raymond E.; and Gadol, Steven M., "Syntheses of Cationic and Zwitterionic Cyclobutadiene Compounds of Cobalt(I). Crystal and Molecular Structure of Tricarbonyl(.eta.-1-methoxy-3-methyl-2-phenylcyclobutadiene)cobalt(1+) Hexafluorophosphate" (1982). Chemistry Faculty Research and Publications. 871.
https://epublications.marquette.edu/chem_fac/871
Comments
Organometallics, Vol. 1, No. 6 (1982): 812-819. DOI.