Addition of Amines to a Carbonyl Ligand: Syntheses, Characterization, and Reactivities of Iridium(III) Porphyrin Carbamoyl Complexes
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https://figshare.com/articles/dataset/Addition_of_Amines_to_a_Carbonyl_Ligand_Syntheses_Characterization_and_Reactivities_of_Iridium_III_Porphyrin_Carbamoyl_Complexes/2298502
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资源简介：
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 carbonyl complexes [(TTP)Ir(NH2R)(CO)]BF4 (7a,b) and [(TTP)Ir(1-MeIm)(CO)]BF4 (8), respectively. In contrast, the carbamoyl
complexes (TTP)Ir(L)[C(O)NHR] (L = P(OEt)3 (5a), PMe2Ph (6a,c)) reacted with
HBF4 to afford the complexes [(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10), respectively. The carbamoyl complexes (TTP)Ir(L)[C(O)NHR]
(L = RNH2 (2a–d), 1-MeIm
(4a), P(OEt)3 (5b), PMe2Ph (6c)) reacted with methyl iodide to give the iodo
complexes (TTP)Ir(L)I (L = RNH2 (11a–d), 1-MeIm (12), P(OEt)3 (13), PMe2Ph (14)). Reactions of the complexes
[(TTP)Ir(PMe2Ph)]BF4 (9) and [(TTP)IrP(OEt)3]BF4 (10) with [Bu4N]I,
benzylamine (BnNH2), and PMe2Ph afforded (TTP)Ir(PMe2Ph)I (14), (TTP)Ir[P(OEt)3]I (13), [(TTP)Ir(PMe2Ph)(NH2Bn)]BF4 (16), and trans-[(TTP)Ir(PMe2Ph)2]BF4 (17), respectively.
Metrical details for the molecular structures of 4a and 17 are reported.
创建时间：
2014-05-12
