Epoxy compounds usually have stronger nucleophilic ability, because the alkyl group on the oxygen atom makes the bond angle smaller, which makes the lone pair of electrons react more dissimilarly with the electron-deficient system. Compound: Tris(triphenylphosphine)chlororhodium, is researched, Molecular C54H45ClP3Rh, CAS is 14694-95-2, about Rhodium assisted peri-C-H activation in benzothiazolyl-hydrazone derivatized pyrene.SDS of cas: 14694-95-2.
Benzothiazolyl hydrazones incorporating polyaromatic pyrene moiety, 1 (H2LPyr), were smartly employed as a directing group (DG) to bring about the Rh assisted C-H bond activation at the peri position of pyrene. The formation of peri-metalated [Rh(LPyr)(H)(PPh3)2] 3 is a logical consequence of its coproduct, a dihalo complex [Rh(HLPyr)Cl2(PPh3)2] 2, in due course of the reaction between the ligand and Wilkinson’s catalyst. The initial formation of the complex 2 in the initial stage of the reaction was envisaged as the driving force for the generation of organometallic complex 3, where paucity of chloride ion triggers the tridentate coordination mode [LPyr]2-via in situ C-H activation. The underlying mechanism of formation of 3 proceeds via oxidative addition, involving a two electron transfer from the appropriate electron reservoir [Rh(I)] to the ligand scaffold and this is accompanied by an intramol. ligand to metal hydride transfer via a PCET pathway. Complexes 2 and 3 are redox active and are prone to oxidation at moderate potentials where the responses are analyzed to be exclusively ligand-centered in nature. Significantly, cyclometalated complex is more prone to oxidation relative to the nonactivated compound, 2. The redox event was meticulously scrutinized by DFT, revealing the destabilization of HOMO in 3 by ∼0.5 eV in comparison to 2. Both complexes provide rich optoelectronic features that were analyzed to be predominantly 1ILCT in nature.
《Rhodium assisted peri-C-H activation in benzothiazolyl-hydrazone derivatized pyrene》 provides a strategy for the preparation of materials with excellent comprehensive properties, which is conducive to broaden the application field of this compound(Tris(triphenylphosphine)chlororhodium)SDS of cas: 14694-95-2.
Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate