Addition of Amines to a Carbonyl Ligand: Syntheses, Characterization, and Reactivities of Iridium(III) Porphyrin Carbamoyl Complexes

Autor:	Taiwo O. Dairo, L. Keith Woo, Arkady Ellern, Robert J. Angelici
Rok vydání:	2014
Předmět:	Organic Chemistry Cationic polymerization Dimethylphenylphosphine chemistry.chemical_element Ligand (biochemistry) Medicinal chemistry Porphyrin Inorganic Chemistry chemistry.chemical_compound chemistry Organic chemistry Iridium Protonolysis Physical and Theoretical Chemistry Octane Quinuclidine
Zdroj:	Organometallics. 33:2266-2276
ISSN:	1520-6041 0276-7333
Popis:	Treatment of (carbonyl)chloro(meso-tetra-p-tolylporphyrinato)iridium(III), (TTP)Ir(CO)Cl (1), with excess primary amines at 23 °C in the presence of Na2CO3 produces the trans-amine-coordinated iridium carbamoyl complexes (TTP)Ir(NH2R)[C(O)NHR] (R = Bn (2a), n-Bu (2b), i-Pr (2c), t-Bu (2d)) with isolated yields up to 94%. The trans-amine ligand is labile and can be replaced with quinuclidine (1-azabicyclo[2.2.2]octane, ABCO), 1-methylimidazole (1-MeIm), triethyl phosphite (P(OEt)3), and dimethylphenylphosphine (PMe2Ph) at 23 °C to afford the hexacoordinated carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (for R = Bn: L = ABCO (3a), 1-MeIm (4a), P(OEt)3 (5a), PMe2Ph (6a)). On the basis of ligand displacement reactions and equilibrium studies, ligand binding strengths to the iridium metal center were found to decrease in the order PMe2Ph > P(OEt)3 > 1-MeIm > ABCO > BnNH2 ≫ Et3N, PCy3. The carbamoyl complexes (TTP)Ir(L)[C(O)NHR] (L = RNH2 (2a,b), 1-MeIm (4a)) undergo protonolysis with HBF4 to give the cationic carbon...
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::2a294e9f8c0c21905936b4e7894c6a31 https://doi.org/10.1021/om500189a Zobrazit plný text záznamu