Synthesis, Theoretical Study and Catalytic Application of Oxidometal (Mo or V) Complexes: Unexpected Coordination Due to Ligand Rearrangement through Metal‐Mediated C–C Bond Formation1. Issue 10 (7th March 2016)

• Record Type: Journal Article
• Authors: Pasayat, Sagarika; Böhme, Michael; Dhaka, Sarita; Dash, Subhashree P.; Majumder, Sudarshana; Maurya, Mannar R.; Plass, Winfried; Kaminsky, Werner; Dinda, Rupam
• Is Part Of: European journal of inorganic chemistry. Issue 10(2016)
• Page Start: 1604
• Page End: 1618
• Publication Date: 2016-03-07
• Subjects: Molybdenum -- Vanadium -- Homogeneous catalysis -- C–C coupling -- Epoxidation -- DFT studies -- Ligand effects -- Schiff bases; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501465
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Two novel dioxidomolybdenum(VI) complexes [MoO2 L′ 1 ] (1 ) and [MoO2 L′ 2 ] (2 ) containing the MoO2 2+ motif with unexpected coordination motifs due to ligand rearrangement through Mo‐mediated interligand C–C bond formation are reported. The ligands (H2 L′ 1–2 ) are tetradentate C–C‐coupled O2 N2 ‐donor systems formed in situ during synthesis of the complexes by reaction of [Mo VI O2 (acac)2 ] with Schiff base ligands of 2‐aminophenol with 2‐pyridinecarbaldehyde (HL 1 ) and 2‐quinolinecarbaldehyde (HL 2 ). To confirm that the ligand rearrangement is assisted by molybdenum, the corresponding vanadium complexes [VO2 L 1 ] (3 ) and [VO2 L 2 ] (4 ) containing original Schiff base ligand (HL 1, 2 ) are also reported here. All complexes1 –4 are characterized by several physicochemical techniques and the structural features of1 and2 have been solved by X‐ray crystallography. The proposed mechanism of molybdenum‐mediated interligand C–C bond formation is supported by DFT calculations including the comparisons with the synthesized vanadium analogues. The catalytic potentials of1 –4 for the epoxidation of styrene and cyclohexene have also been explored. Abstract : Two unique dioxidomolybdenum(VI) complexes [MoO2 L′ 1–2 ] (1 and2 ) containing ligands generated by metal‐mediated interligand C–C bond formation are reported and are investigated by DFT calculations. Unique observations not found in the corresponding vanadium(V) complexes [VO2 L 1–2 ] (3 and4 ) and the catalytic potentials of1 –4 are disclosed.