Issue 29, 2019

Solvent-tailored Pd3P0.95 nano catalyst for amide–nitrile inter-conversion, the hydration of nitriles and transfer hydrogenation of the C[double bond, length as m-dash]O bond

Abstract

For the first time, a one pot thermolysis of [Pd(PPh3)2Cl2] prepared by reacting Ph3P with PdCl2 in a 2 : 1 molar ratio in MeOH at 280 °C in a trioctylphosphine (TOP) and oleylamine(OA)-octadecane(ODE) mixture (1 : 1) was used to prepare quantum dots (QDs; size ∼2–3 nm) and nanoparticles (NPs; size ∼13–14 nm), respectively, of composition Pd3P0.95. TEM, SEM-EDX, powder-XRD and XPS (for QDs only) were used to authenticate the two nanophases. 31P{1H}NMR experiments performed to monitor the progress of thermolysis reactions revealed that the phosphorus present in the Pd3P0.95 QDs had come from TOP, whereas in Pd3P0.95 NPs, its source is triphenylphosphine. The nature of the solvent did not affect the chemical composition of the nano-phase but controlled its size. Probably, solvent dependent, unique, single source precursors (SSPs) of palladium were generated in situ, and controlled the size. The catalytic activity of both Pd3P0.95 QDs and NPs was explored. The QDs were found to be efficient as a catalyst for the amide–nitrile interconversion at room temperature (yield up to 92% in 4 h), hydration of nitriles and transfer hydrogenation (TH) of carbonyl compounds with yields up to 96% in 3–4 h. The yields and reaction rates of amide–nitrile inter-conversion and TH when catalyzed by Pd3P0.95 QDs were found to be higher compared to the ones observed with the Pd/C catalyst. The binding energy of Pd(3d) in the X-ray photoelectron spectrum (XPS) of Pd3P0.95 indicated an electron transfer from the metal to phosphorus, resulting in electron deficient palladium, which facilitates the coordination of a substrate to Pd and drives the reaction. The reusability of Pd3P0.95 QDs for the interconversion was found to be up to 4-times, while for the transfer hydrogenation of carbonyl compounds it was up to 6-times, but with a diminished yield. Pd3P0.95 NPs were found to be less active (yield up to 36% in optimized reaction conditions) in comparison to Pd3P0.95 QDs. The mercury poisoning test suggested that the catalysis predominantly proceeded heterogeneously on the surface of the QDs. The PXRD and XPS results did not suggest a significant variation in the phase of QDs after the third catalytic cycle. The bleeding of Pd during catalysis (determined by flame AAS) and the agglomeration of QDs as supported by the SEM-EDX and TEM results are probably responsible for the reduction in the catalytic activity of QDs after reusing three times.

Graphical abstract: Solvent-tailored Pd3P0.95 nano catalyst for amide–nitrile inter-conversion, the hydration of nitriles and transfer hydrogenation of the C [[double bond, length as m-dash]] O bond

Supplementary files

Article information

Article type
Paper
Submitted
26 Nov. 2018
Accepted
22 Maijs 2019
First published
22 Maijs 2019

Dalton Trans., 2019,48, 10962-10970

Solvent-tailored Pd3P0.95 nano catalyst for amide–nitrile inter-conversion, the hydration of nitriles and transfer hydrogenation of the C[double bond, length as m-dash]O bond

A. K. Sharma, H. Joshi, R. Bhaskar and A. K. Singh, Dalton Trans., 2019, 48, 10962 DOI: 10.1039/C8DT04667K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements