Mechanism of thermal ring closure of metal pentacarbonyl complexes, M(CO)5L (L = bidentate ligand), produced during photolysis of Group 6 hexacarbonyl complexes
| Autor: | R. Van Eldik, K. Bal Reddy |
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| Rok vydání: | 1990 |
| Předmět: |
Steric effects
Stereochemistry Organic Chemistry Photodissociation Center (category theory) Ethylenediamine Homogeneous catalysis Ring (chemistry) Chemical reaction Inorganic Chemistry Metal chemistry.chemical_compound Crystallography chemistry visual_art visual_art.visual_art_medium Physical and Theoretical Chemistry |
| Zdroj: | Organometallics. 9:1418-1421 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om00119a011 |
| Popis: | The kinetics of the thermal ring-closure reactions of M(CO){sub 5}L, produced during the photolysis of M(CO){sub 6}/L for L = ethylenediamine (en) and 1,4-diisopropyl-1,4-diazabutadiene (dab), were studied as a function of (L), temperature, and pressure. The values of {Delta}S{double dagger} and {Delta}V{double dagger} are significantly negative, {minus}40 to {minus}170 J K{sup {minus}1} mol{sup {minus}1} and {minus}5.4 to {minus}13.7 cm{sup 3} mol{sup {minus}1}, respectively, for M = Cr (L = en) and M = Mo, W (L = en, dab) and support an associative ring-closure mechanism. The results demonstrate the crucial role played by the size of the metal center and the steric hindrance on L. |
| Databáze: | OpenAIRE |
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