Double Carbonyl Substitution in [BrMn(CO)5]: Reaction with Benzoylhydrazine and Synthesis of fac‐[Mn(Br)(CO)3(BHD)]·2THF (BHD = OC(Ph)—NH—NH2) |
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Authors: | Gelson Manzoni de Oliveira,Gleison Antonio Casagrande,Eliandro Faoro,Ram o Marceli Fernandes Jr.,Peter Mayer,Ernesto Schulz Lang |
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Affiliation: | Gelson Manzoni de Oliveira,Gleison Antonio Casagrande,Eliandro Faoro,Ramão Marceli Fernandes Jr.,Peter Mayer,Ernesto Schulz Lang |
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Abstract: | [BrMn(CO)5] reacts with benzoylhydrazine in THF occurring substitution of two CO groups by a Metal‐ligand ring to give fac‐[Mn(Br)(CO)3(BHD)]·2THF (BHD = C6H5CONHNH2). The novel compound shows a distorted octahedral arrangement at the manganese atom, with three nearly linear carbonyl ligands in a fac arrangement, illustrating another example that the CO group in position trans to the bromine ligand in [BrMn(CO)5] presents the most intensive metal‐CO backbonding effect of all the CO groups of the parent complex, leading to the formation of a facial (and not meridional) isomer, even in the presence of a bidentate ligand like benzydrazide. X‐ray measures of yellow crystals showed that the title complex belong to space group P21/c, with the asymmetric unit containing one crystallographically independent [Mn(Br)(CO)3(BHD)] complex and two tetrahydrofurane solvate molecules. The new compound represents heretofore the unique occurrence of the complexing single bidentate ligand ‐O=C(Ph)‐N(H)‐N(H)2‐ with an octahedral coordination at the MnI atom supported chiefly by carbonyl groups. |
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Keywords: | Manganese Carbonyl‐benzoylhydrazone complexes Carbonyl substitution fac/mer‐Isomery |
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