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Insertions of Allenes into Palladium-Carbon Bonds of Complexes Containing Bidentate Nitrogen Ligands. Structural and Mechanistic Studies
| Content Provider | Semantic Scholar |
|---|---|
| Author | Delis, J. G. P. Groen, J. H. Leeuwen, P. Van Vrieze, Kees Veldman, Nora Spek, Anthony L. |
| Copyright Year | 1997 |
| Abstract | The insertion reactions of the allenes propadiene and 1,2-heptadiene in the Pd−C bond of complexes (N⌒N)Pd(R)X (N⌒N = 8-PQ, p-An-BIAN, i-Pr-DAB, p-An-DAB, i-Pr-PyCa; R = Me, C(O)Me, C(O)Ph, C(O)i-Pr; X = Cl, Br) have been investigated. An X-ray crystal structure determination of (8-PQ)Pd{(1−3-η)-2-methylpropenyl}Cl exhibited the unexpected monodentate coordination of the nitrogen ligand. The monodentate coordination in apolar solvents and bidentate coordination in polar solvents was demonstrated by means of NOE NMR experiments. Kinetic measurements revealed that the reactions are first order in the palladium concentration and occur via an allene concentration independent and dependent pathway. Reactions of complexes containing flexible bidentate nitrogen ligands were retarded by additional free bidentate nitrogen ligand indicating that initial dissociation of a nitrogen donor is an important step in the reaction. We have strong indications that the migration of the R group to the precoordinated allene is ... |
| Starting Page | 551 |
| Ending Page | 562 |
| Page Count | 12 |
| File Format | PDF HTM / HTML |
| DOI | 10.1021/om960790e |
| Volume Number | 16 |
| Alternate Webpage(s) | https://pure.uva.nl/ws/files/3654169/2427_24744y.pdf |
| Alternate Webpage(s) | https://doi.org/10.1021/om960790e |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
