Flexible interactions of the rare-earth elements Y, La, and Lu with phosphorus in metallacyclohexane rings.
Chem Sci
; 15(30): 12138-12147, 2024 Jul 31.
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| ID: mdl-39092093
ABSTRACT
A geometrically flexible bifunctional (bis)aminophosphine ligand was synthesized in a three-component, one-pot Kabachnik-Fields reaction using tert butylphosphine, paraformaldehyde, and 3,5-dimethyl aniline. The product, bis((3,5-dimethylphenyl)aminomethyl) tert butylphosphine (ArBiAMP t Bu), containing two secondary amines and a tertiary phosphine, was isolated in good yields. Deprotonation of both N-H groups with (trimethylsilyl)methylpotassium (K-CH2SiMe3), followed by salt metathesis with LaI3, YI3, and LuI3 generated the corresponding MI(ArBiAMP t Bu)(thf)3 complexes (M = Y (1), La (2), and Lu (3)) in good yields. A sterically encumbered indene, 1,3-diisopropyl-4,7-dimethyl-1H-indene, iPrMeInd, was deprotonated in situ and installed via salt-metathesis to generate the organometallic series of η5-indenide complexes, M(ArBiAMP t Bu)(η5-iPrMeInd)(thf) (M = Y (4), La (5), and Lu (6)). 1H, 31P, 13C, and 89Y NMR experiments, IR spectroscopy, and single crystal X-ray diffraction (SC-XRD), were used to characterize these complexes. The Y-P coupling constant was found to be variable depending on the modifiable coordination environment of the metal center, indicating potential as both a spectroscopic handle as well as providing insight into the influence of additional ligands on the metal center.
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Chem Sci
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2024
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Article