The X-ray structure of the hydroxycarbene complex [(DPPP)(CO)3MnC(OH)CH3]+[CF3SO3]− {facial-[1,3-bis(diphenylphosphino)propane(methyl-hydroxycarbene) tricarbonylmanganese(I)]} triflate
| Autor: | Milton Orchin, Douglas M. Ho, Philip L. Motz |
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| Rok vydání: | 1991 |
| Předmět: |
Stereochemistry
Hydrogen bond 1 3-Bis(diphenylphosphino)propane Organic Chemistry Crystal structure Biochemistry Inorganic Chemistry chemistry.chemical_compound Crystallography chemistry Alkane stereochemistry Materials Chemistry Moiety Physical and Theoretical Chemistry Carbene Conformational isomerism Trifluoromethanesulfonate |
| Zdroj: | Journal of Organometallic Chemistry. 407:259-269 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/0022-328x(91)86123-8 |
| Popis: | The cationic octahedral manganese(I) hydroxycarbene complex [(DPPP)(CO) 3 MnC(OH)CH 3 ] + ] has been synthesized and isolated as its triflate salt, and its structure fully determined by X-ray diffraction. A comparison of our cationic Mn 1 methylhydroxycarbene complex to the neutral isoelectronic Cr 0 and Mo 0 phenylhydroxycarbene structures reported in the literature reveals a number of surprising differences and similarities. In the Cr and Mo complexes the metal fragment and the hydroxy hydrogen are positioned syn ( Z -isomer) giving the conformational isomer often seen in alkoxycarbenes. In contrast, in our Mn complex, these substituents are found in the alternate anti conformation ( E -isomer). In addition, dimers are observed in the solid state due to a much more intricate network of hydrogen bonds. Nevertheless, in each of these octahedral isoelectronic hydroxycarbene complexes, the orientation of the memtal framework and the carbene moiety with respect to each other is remarkably similar. A twist of approximately 34° about the MC(carbene) bond and away from the fully eclipsed electronically favored geometry is observed in all three complexes. |
| Databáze: | OpenAIRE |
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