| Autor: |
Kunchur HS; Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India., Sonawane SC; Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India., Saini P; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India., Ramakrishnan S; Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India., Balakrishna MS; Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India. |
| Abstrakt: |
The reactions of amide functionalized bisphosphine, o -Ph 2 PC 6 H 4 C-(O)N(H)C 6 H 4 PPh 2 - o ( 1 ) (BalaHariPhos), with copper salts is described. Treatment of 1 with CuX in a 1:1 molar ratio yielded chelate complexes of the type [CuX{( o -Ph 2 PC 6 H 4 C(O)N(H)C 6 H 4 PPh 2 - o )}-κ 2 -P,P ] (X = Cl, 2 ; Br, 3 ; and I, 4 ), which on subsequent treatment with KO t Bu resulted in a dimeric complex [Cu( o -Ph 2 PC 6 H 4 C(O)(N)C 6 H 4 PPh 2 - o )] 2 ( 5 ). Interestingly, complexes 2 - 4 showed weak N-H···Cu interactions. These weak H-bonding interactions are studied in detail both experimentally and computationally. Also, Cu I complexes 2 - 5 were employed in the oxidative dehydrogenative carboxylation (ODC) of unactivated cycloalkanes in the presence of carboxylic acids to form the corresponding allylic esters. Among complexes 2 - 5 , halide-free dimeric Cu I complex 5 showed excellent metal-ligand cooperativity in the oxidative dehydrogenative carboxylation (ODC) in the presence of carboxylic acids to form the corresponding allylic esters through C( sp 3 )-H bond activation of unactivated cycloalkanes. Mechanistic details of the catalytic process were established by isolating the precatalyst [Cu{( o -Ph 2 PC 6 H 4 C(O)(NH)C 6 H 4 PPh 2 - o )-κ 2 -P,P }(OOCPh)] ( 6 ) and fully characterized by mass spectrometry, NMR data, and single-crystal X-ray analysis. Density functional theory-based calculations further provided a quantitative understanding of the energetics of a series of H atom transfer steps occurring in the catalytic cycle. |
