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- Title
Ligand influence on intramolecular cyclometalation in bis(phosphinimine) rare earth alkyl complexes.
- Authors
Johnson, Kevin R.D.; Kamenz, Breanne L.; Hayes, Paul G.
- Abstract
The synthesis and reactivity of two new bis(phosphinimine)carbazole ligands (PippN=PMe2)2DMC (H LA, 3) and (PippN=P(C4H8))2DMC (H LB, 10), where Pipp = para-isopropylphenyl and DMC = 3,6-dimethylcarbazole, are reported. Dialkyl lutetium complexes of 3 and 10 were prepared in the presence of DMAP and THF by reaction of the proteo ligands with the new trialkyl reagent, Lu(CH2SiMe3)3(DMAP)2 ( 4) as well as Lu(CH2SiMe3)3(THF)2. For both ligands 3 and 10, the resulting lutetium complexes were prone to intramolecular cyclometalative alkane elimination reactions whereby the location of cyclometalation was influenced by the identity of the ancillary ligand coordinated to the metal. For ligand 3, cyclometalation of two PMe2 groups generated the complex ( LA-κ3 N,κ2 C)Lu(DMAP)2 ( 5), whereas ligand 10 resulted in the single ortho-metalation of a para-isopropylphenyl ring to afford ( LB-κ3 N,κ C)Lu(CH2SiMe3) ( 12). When complexed with scandium, ligand 10 behaved differently; double cyclometalation of two phospholane moieties resulted in the species ( LB-κ3 N,κ2 C)Sc ( 15). The nature of the cyclometalation reactivity of ligands 3 and 10 is supported by X-ray crystallography and kinetic analysis, respectively.
- Subjects
MOLECULAR structure of ligands; PHOSPHINIMINES; SCANDIUM; LUTETIUM; PHENYL compounds
- Publication
Canadian Journal of Chemistry, 2016, Vol 94, Issue 4, p330
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/cjc-2015-0368