Ligand-Directed Assembly of Multimetallic Aluminum Complexes: Synthesis, Structure and ROP Catalysis


Por: García-López J.-D., García-Álvarez A.-C., Hernández-Balderas U., Gallardo-Garibay A., Jancik V., Martínez-Otero D., Moya-Cabrera M.

Publicada: 1 ene 2024
Resumen:
Multinuclear aluminum complexes are useful catalysts for the ring opening polymerization (ROP) of ?-caprolactone (?-CL), often outperforming monometallic analogues in the production of biodegradable polycaprolactone (PCL). These complexes require control over metal-metal distance, ligand structure, and substituents. Herein, we report on the preparation of mono-, bi-, and octametallic aluminum complexes through direct chelation of multidentate bis(phosphino)-2,2-dimethyl-1,3-diamino ligands Me2C[CH2NHR2P(O)]2; R=Ph(1), iPr(2), tBu(3). Ligands 1–3 yielded bimetallic complexes with two types of coordination pockets, as well as bimetallic systems with identical coordination environments. In addition to the diversity of structural patterns within the present series, the catalytic performances of [AlR2{?2-N,N’,–(Me2C{CH2NPh2P(O)}2}-(?2-O,O’-AlR2)] (R=Me(4), Et(5), iBu(6)) outperformed that of the monometallic [AlEt2{?2-O,O’-(Me2C(CH2NtBu2P(O))2H} (10), showing controlled and immortal ROP of ?-CL in the presence of BnOH as co-initiator. DFT calculations suggest that the primary active site for 4–6 is the N-Al–N center. Gaining insight into the underlying principles that lead to high activity and controlled production of PCL in bimetallic systems can help design tailor-made complexes with enhanced performance. © 2024 The Authors. European Journal of Inorganic Chemistry published by Wiley-VCH GmbH.

Filiaciones:
García-López J.-D.:
 Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carretera Toluca-Atlacomulco Km 14.5, Toluca, Estado de México, 50200, Mexico

García-Álvarez A.-C.:
 Universidad Nacional Autónoma de México, Instituto de Química, Circuito Exterior s/n, Ciudad Universitaria, Cd. Mex, 04510, Mexico

Hernández-Balderas U.:
 Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carretera Toluca-Atlacomulco Km 14.5, Toluca, Estado de México, 50200, Mexico

 Universidad Nacional Autónoma de México, Instituto de Química, Circuito Exterior s/n, Ciudad Universitaria, Cd. Mex, 04510, Mexico

Gallardo-Garibay A.:
 Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carretera Toluca-Atlacomulco Km 14.5, Toluca, Estado de México, 50200, Mexico

 Universidad Nacional Autónoma de México, Instituto de Química, Circuito Exterior s/n, Ciudad Universitaria, Cd. Mex, 04510, Mexico

Jancik V.:
 Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carretera Toluca-Atlacomulco Km 14.5, Toluca, Estado de México, 50200, Mexico

 Universidad Nacional Autónoma de México, Instituto de Química, Circuito Exterior s/n, Ciudad Universitaria, Cd. Mex, 04510, Mexico

Martínez-Otero D.:
 Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carretera Toluca-Atlacomulco Km 14.5, Toluca, Estado de México, 50200, Mexico

 Universidad Nacional Autónoma de México, Instituto de Química, Circuito Exterior s/n, Ciudad Universitaria, Cd. Mex, 04510, Mexico

Moya-Cabrera M.:
 Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Carretera Toluca-Atlacomulco Km 14.5, Toluca, Estado de México, 50200, Mexico

 Universidad Nacional Autónoma de México, Instituto de Química, Circuito Exterior s/n, Ciudad Universitaria, Cd. Mex, 04510, Mexico
ISSN: 14341948
Editorial
Wiley-VCH Verlag, COMMERCE PLACE, 350 MAIN ST, MALDEN 02148, MA USA, Alemania
Tipo de documento: Article
Volumen: 27 Número: 33
Páginas:
WOS Id: 001411967300010
imagen hybrid

MÉTRICAS