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- Title
Unprecedented Ring-Ring Interconversion of N,P,C-Cage Ligands.
- Authors
Villalba Franco, José Manuel; Schnakenburg, Gregor; Espinosa Ferao, Arturo; Streubel, Rainer
- Abstract
The novel N,P,C-cage complexes 5 a- f and 6 a- f have been obtained by the reaction of the P-pentamethylcyclopentadienylphosphinidene complex 2, generated thermally from 2 H-azaphosphirene complex 1, with N-methyl- C-arylcarbaldimines 3 a- f. Li/Cl phosphinidenoid complex 8 reacted with 3 a, b to give N,P,C-cage complexes 6 a, b, whereas with 3 c- f, complexes 6 c- f were obtained in negligible amounts only. Both types of ligand N,P,C-cage structures 5 and 6 were found to be in an unprecedented equilibrium, with 5 a, f as the predominant species. Transient electrophilic terminal phosphinidene complexes 10 a- f serve as intermediates in both ligand interconversions ( 5 a, f↔ 6 a, f), as evidenced through trapping reactions with phenylacetylene and N-methyl- C-phenylcarbaldimine, thus leading to the novel N,P,C-cage complexes 13 b and 15. DFT calculations predicted a small difference in the relative energies of the two types of N,P,C-cage ligands, and a remarkable stabilisation of the aminophosphinidene complex 10 as the common precursor, thereby providing an insight into this surprising 5-ring-3-ring interconversion. In depth analysis of intermediate 10 revealed the occurrence of both through-bond (conventional inductive/mesomeric effects) and through-space (non-covalent interactions) mechanisms, which amount to 67.8 and 14.4 kcal mol−1, respectively, and account for the remarkable stabilisation of this intermediate.
- Subjects
LIGAND exchange reactions; COORDINATION compounds; CLATHRATE compounds; COMPLEX compounds; CHEMICAL bonds; CHEMICAL research
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 9, p3727
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201405754