title: Palladium-phosphorus/sulfur nanoparticles (NPs) decorated on graphene oxide: synthesis using the same precursor for NPs and catalytic applications in Suzuki-Miyaura coupling.
abstract: PdP2 and Pd4S nanoparticles (NPs) (size: ∼2-6 and 9-15 nm respectively) have been prepared for the first time from a single source precursor complex [Pd(L)Cl2] (1) by its one pot thermolysis at 200 °C in TOP and OA/ODE (1 : 1) respectively. These NPs were stirred with graphene oxide (GO) at room temperature to prepare NP composites, GO-PdP2 and GO-Pd4S. The GO-PdP2 NPs have been synthesized for the first time. The thioether ligand L prepared by reaction of 1,3-dibromo-2-propanol with the in situ generated PhSNa reacts with [PdCl2(CH3CN)2] in CH3CN at 70 °C resulting in 1. The L and 1 have been characterized by (1)H and (13)C{(1)H} NMR and HR-MS. The single crystal structure of 1 determined by X-ray diffraction reveals nearly square planar geometry around the Pd metal centre. The catalytic activities of two palladium nano-phases having phosphorus and sulphur respectively as a co-constituent for Suzuki-Miyaura coupling have been found to be exceptionally different, as PdP2 nanoparticles (NPs) grafted on graphene oxide (GO-PdP2) are significantly more efficient than Pd4S NPs grafted on GO. Without grafting PdP2 and Pd4S both have low efficiency. This is the first report comparing the influence of P and S on the catalytic activity of Pd NPs. TEM, SEM-EDX and powder-XRD have been used to authenticate all NPs. The GO-PdP2 NPs have been found to be efficient catalysts for Suzuki-Miyaura coupling reactions (yield up to 96% in 30 min) at room temperature to 80 °C. Their recyclability has been found up to 6 cycles. In contrast, GO-Pd4S NPs are little active in comparison with GO-PdP2 NPs. The size of NPs and their distribution on GO appear to be key factors affecting the catalytic efficiency of the composite NPs. Leaching of Pd from GO-PdP2 NPs contributes significantly to the catalysis as evidenced by the three phase test, hot-filtration and recycling experiments. The catalysis is almost homogeneous.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Delhi, New Delhi 110016, India. aksingh@chemistry.iitd.ac.in ajai57@hotmail.com.
authors.forename: Hemant
authors.initials: H
authors.lastname: Joshi
authors.forename: Kamal Nayan
authors.initials: KN
authors.lastname: Sharma
authors.forename: Alpesh K
authors.initials: AK
authors.lastname: Sharma
authors.forename: Ajai Kumar
authors.initials: AK
authors.lastname: Singh