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Genesis of electron deficient Pt1(0) in PDMS-PEG aggregates.

ABSTRACT: While numerous single atoms stabilized by support surfaces have been reported, the synthesis of in-situ reduced discrete metal atoms weakly coordinated and stabilized in liquid media is a more challenging goal. We report the genesis of mononuclear electron deficient Pt1(0) by reducing H2PtCl6 in liquid polydimethylsiloxane-polyethylene glycol (PDMS-PEG) (Pt1@PDMS-PEG). UV-Vis, far-IR, and X-ray photoelectron spectroscopies evidence the reduction of H2PtCl6. CO infrared, and 195Pt and 13C NMR spectroscopies provide strong evidence of Pt1(0), existing as a pseudo-octahedral structure of (R1OR2)2Pt(0)Cl2H2 (R1 and R2 are H, C, or Si groups accordingly). The weakly coordinated (R1OR2)2Pt(0)Cl2H2 structure and electron deficient Pt1(0) have been validated by comparing experimental and DFT calculated 195Pt NMR spectra. The H+ in protic state and the Cl- together resemble HCl as the weak coordination. Neutralization by a base causes the formation of Pt nanoparticles. The Pt1@PDMS-PEG shows ultrahigh activity in olefin hydrosilylation with excellent terminal adducts selectivity.

SUBMITTER: Liu K

PROVIDER: S-EPMC6397160 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Genesis of electron deficient Pt1(0) in PDMS-PEG aggregates.

Liu Kairui K Hou Guangjin G Mao Jingbo J Xu Zhanwei Z Yan Peifang P Li Huixiang H Guo Xinwen X Bai Shi S Zhang Z Conrad ZC

Nature communications 20190301 1

While numerous single atoms stabilized by support surfaces have been reported, the synthesis of in-situ reduced discrete metal atoms weakly coordinated and stabilized in liquid media is a more challenging goal. We report the genesis of mononuclear electron deficient Pt1(0) by reducing H2PtCl6 in liquid polydimethylsiloxane-polyethylene glycol (PDMS-PEG) (Pt1@PDMS-PEG). UV-Vis, far-IR, and X-ray photoelectron spectroscopies evidence the reduction of H<s ...[more]

PMID: 30824847

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Project description:We report the synthesis, crystal structures and magnetic properties of the giant heterometallic [Mn36Ni4]2-/0 (compounds 1, 2)/[Mn32Co8] (compound 3) "loops-of-loops-and-supertetrahedra" molecular aggregates and of a [Mn2Ni6]2+ compound (cation of 4) that is structurally related with the cation co-crystallizing with the anion of 1. In particular, after the initial preparation and characterization of compound [Mn2Ni6(μ4-O)2(μ3-OH)3(μ3-Cl)3(O2CCH3)6(py)8]2+[Mn36Ni4(μ4-O)8(μ3-O)4(μ3-Cl)8Cl4(O2CCH3)26(pd)24(py)4]2- (1) we targeted the isolation of (i) both the cationic and the anionic aggregates of 1 in a discrete form and (ii) the Mn/Co analog of [Mn36Ni4]2- aggregate. Our synthetic efforts toward these directions afforded the discrete [Mn36Ni4] "loops-of-loops-and-supertetrahedra" aggregate [Mn36Ni4(μ4-O)8(μ3-O)4(μ3-Cl)8Cl2(O2CCH3)26(pd)24(py)4(H2O)2] (2), the heterometallic Mn/Co analog [Mn32Co8(μ4-O)8(μ3-O)4(μ3-Cl)8Cl2(μ2-OCH2CH3)2(O2CCH3)28(pd)22(py)6] (3) and the discrete [Mn2Ni6]2+ cation [Mn2Ni6(μ4-O)2(μ3-OH)4(μ3-Cl)2(O2CCH3)6(py)8](ClO4)(OH) (4). The structure of 1 consists of a mixed valence [ Mn28III Mn8II Ni4II ]2- molecular aggregate that contains two Mn8III Ni2II loops separated by two Mn6III Mn4II supertetrahedral units and a [ Mn2III Ni6II ]2+ cation based on two [MnIII Ni3II (μ4-O)(μ3-OH)1.5(μ3-Cl)1.5]4+ cubane sub-units connected through both mono- and tri-atomic bridges provided by the μ4-O2- and carboxylate anions. The structures of 2-4 are related to those of the compounds co-crystallized in 1 exhibiting however some differences that shall be discussed in detail in the manuscript. Magnetism studies revealed the presence of dominant ferromagnetic interactions in 1-3 that lead to large ground state spin (ST) values for the "loops-of-loops-and-supertetrahedra" aggregates and antiferromagnetic exchange interactions in 4 that lead to a low (and possibly zero) ST value. In particular, dc and ac magnetic susceptibility studies revealed that the discrete [Mn36Ni4] aggregate exhibits a large ST value ~ 26 but is not a new SMM. The ac magnetic susceptibility studies of the [Mn32Co8] analog revealed an extremely weak beginning of an out-of-phase tail indicating the presence of a very small relaxation barrier assignable to the anisotropic Co2+ions and a resulting out-of-phase ac signal whose peak is at very low T.

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Genesis of electron deficient Pt1(0) in PDMS-PEG aggregates.

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Genesis of electron deficient Pt1(0) in PDMS-PEG aggregates.

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