Cyclooctadiene Rh(I) Bis- and Tris(pyrazolyl)aluminate Complexes and Their Catalytic Activity on the Polymerization of Phenylacetylene

Omar J Garcia (1) , Laure Vendier (2) , Michel Etienne (2) , Steven Gwaltney (1) , Abigail Ressler (1) , Miguel-Ángel Muñoz-Hernández (1)

1 Mississippi State University [Mississippi]
2 LCC - Laboratoire de chimie de coordination

In this work, we report the transfer of alkyl bis- and tris(pyrazolyl)aluminates metalloligands to an electron-rich organotransition metal center. The 16-electron heterobimetallic complexes of rhodium [Rh(COD){Al(Ph2pz)2Me2}] (3) and [Rh(COD){Al(Ph2pz)3Me}] (4) were obtained by metathesis reaction of the sodium bis- (1) and tris(pyrazolyl)aluminate (2) with [RhCl(COD)]2. For 3, 1H and 13C NMR in solution along with DFT calculations are consistent with a κ2-coordination mode of the bis(pyrazolyl)aluminate to a square-planar Rh(I) center. The X-ray structure of 4 shows a similar κ2-coordination mode of the tris(pyrazolyl)aluminate to Rh(I) with a pendant pyrazolyl moiety. The attempted synthesis of aluminate-rhodium complexes with R = CF3, tBu on the pyrazolate ring afforded [Rh(R2pz)(COD)]2 and [R2pzAlMe2]2. Complexes 3 and 4 were investigated as homogeneous catalysts in the polymerization of phenylacetylene (PA). Both complexes showed enhanced catalytic activity compared to analogous rhodium poly(pyrazolyl)borates. Optimized gas-phase DFT geometries of 3, 4, [Rh(COD){B(Ph2pz)2Me2}], and [Rh(COD){B(Ph2pz)3Me}] were used to compare bite angles, while DFT geometries of 3-CO, 4-CO, [Rh(CO)2{B(Ph2pz)2Me2}], and [Rh(CO)2{B(Ph2pz)3Me}] were employed to probe the electronic situation of the rhodium center through IR CO stretching modes. The wider bite angles and the less electron-rich rhodium center of the poly(pyrazolyl)aluminates compared with their borate analogues could be implicated in the better performance of the active catalytic species during polymerization of PA.

Mots clés: Chemical structure; Rhodium; Sodium; Ligands; Polymerization

Domaines: Chimie de coordination; Catalyse; Polymères

Omar J Garcia, Laure Vendier, Michel Etienne, Steven Gwaltney, Abigail Ressler, et al.. Cyclooctadiene Rh(I) Bis- and Tris(pyrazolyl)aluminate Complexes and Their Catalytic Activity on the Polymerization of Phenylacetylene. Inorganic Chemistry, 2021, 60 (14), pp.10757-10763. ⟨10.1021/acs.inorgchem.1c01434⟩. ⟨hal-03292668⟩