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Article Dans Une Revue Organometallics Année : 2023

Group IV Complexes with Sterically Congested N -Aryl-adamantylcarbamidate Ligands

Résumé

Metalation of N-(2,6-dibenzhydryl-4-tolyl)adamantane-1-carboxamide (1, Ar*N(H)–C(O)–Ad) with M(NMe2)4 (M = Ti, Zr, Hf) yields amidate complexes Ar*N=C(Ad)–O–Ti(NMe2)3 (2) as well as bis(amidate) compounds (Ar*N=C(Ad)–O)2M(NMe2)2 (M = Zr (3), Hf (4)). In 2, the amidate ligand acts as a monodentate base via the oxygen atom with the Ti center in a slightly distorted tetrahedral environment. The steric requirement of the amidate ligand stabilizes the small coordination number of four of the Ti atom. In congeners 3 and 4, two bidentate amidate ligands exist in the coordination spheres, leading to hexacoordinate group IV metal atoms. The small bite angles of the Zr- and Hf-bound amidate ligands lead to severe distortion of the octahedral environments of the Zr and Hf centers. Titanium compound 2 is an unsuitable choice to catalyze hydrofunctionalization of alkynes with amines and phosphane oxides and despite the significantly smaller pKa value of the carboxylic amide, formation of carboxamide 1 is the dominant reaction upon addition of amines or phosphane oxides to release intramolecular steric strain introduced by the very bulky adamantylamidato ligand.
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Dates et versions

hal-04196519 , version 1 (05-09-2023)

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Bahareh Rezaei Kheirkhah, Wimonsiri Huadsai, Phil Liebing, Sébastien Bontemps, Matthias Westerhausen. Group IV Complexes with Sterically Congested N -Aryl-adamantylcarbamidate Ligands. Organometallics, 2023, 42 (16), pp.2304-2311. ⟨10.1021/acs.organomet.3c00291⟩. ⟨hal-04196519⟩
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