Platinum-Containing Polyoxometalates: Syn- and anti-[PtII2(α-PW11O39)2]10- and Formation of the Metal-Metal-Bonded di-PtIII Derivatives

Zhengguo Lin; Natalya V. Izarova; Aleksandar Kondinski; Xiaolin Xing; Ali Haider; Linyuan Fan; Nina Vankova; Thomas Heine; Bineta Keita; Jie Cao; Changwen Hu; Ulrich Kortz

doi:10.1002/chem.201600555

Platinum-Containing Polyoxometalates: Syn- and anti-[Pt^II₂(α-PW₁₁O₃₉)₂]^10- and Formation of the Metal-Metal-Bonded di-Pt^III Derivatives

Zhengguo Lin, Natalya V. Izarova, Aleksandar Kondinski, Xiaolin Xing, Ali Haider, Linyuan Fan, Nina Vankova, Thomas Heine, Bineta Keita, Jie Cao, Changwen Hu, Ulrich Kortz

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

20 Citations (Scopus)

Abstract

The first examples of dimeric, di-Pt^II-containing heteropolytungstates are reported. The two isomeric di-platinum(II)-containing 22-tungsto-2-phosphates [anti-Pt^II₂(α-PW₁₁O₃₉)₂]^10- (1 a) and [syn-Pt^II₂(α-PW₁₁O₃₉)₂]^10- (2 a) were synthesized in aqueous pH 3.5 medium using one-pot procedures. Polyanions 1 a and 2 a contain a core comprising two face-on PtO₄ units, with a Pt⋯Pt distance of 2.9-3 Å. Both polyanions were investigated by single-crystal XRD, IR, TGA, UV/Vis, ³¹P NMR, ESI-MS, CID-MS/MS, electrochemistry, and DFT. On the basis of DFT and electrochemistry, we demonstrated that the {Pt₂^II} moiety in 1 a and 2 a can undergo fully reversible two-electron oxidation to {Pt₂^III}, accompanied by formation of a single Pt-Pt bond. Hence we have discovered the novel subclass of Pt^III-containing heteropolytungstates.

Original language	English
Pages (from-to)	5514-5519
Number of pages	6
Journal	Chemistry - A European Journal
Volume	22
Issue number	16
DOIs	https://doi.org/10.1002/chem.201600555
Publication status	Published - 2016 Apr 11

Bibliographical note

Funding Information:
U.K. acknowledges the German Science Foundation (DFG, KO- 2288/20-1), the COST Actions CM1203 (PoCheMoN) and CM1006 (EUFEN), and the Chinese Academy of Sciences President's International Fellowship Initiative (Grant No. 2015VMA041). N.V.I. thanks the DFG (IZ-60/1-1) for financial support. We kindly acknowledge Johnson Matthey Plc for a loan of PtII salts. J.C. and C.H. thank the National Natural Science Foundation of China (21371025, 21173021, 21373027), the 111 Project (B07012), and 973 Program (2014CB932103). We acknowledge Dr. Maria Barsukova-Stuckart for some assistance with lab work.

Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

All Science Journal Classification (ASJC) codes

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.201600555

Cite this

Lin, Z., Izarova, N. V., Kondinski, A., Xing, X., Haider, A., Fan, L., Vankova, N., Heine, T., Keita, B., Cao, J., Hu, C., & Kortz, U. (2016). Platinum-Containing Polyoxometalates: Syn- and anti-[Pt^II₂(α-PW₁₁O₃₉)₂]^10- and Formation of the Metal-Metal-Bonded di-Pt^III Derivatives. Chemistry - A European Journal, 22(16), 5514-5519. https://doi.org/10.1002/chem.201600555

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title = "Platinum-Containing Polyoxometalates: Syn- and anti-[PtII2(α-PW11O39)2]10- and Formation of the Metal-Metal-Bonded di-PtIII Derivatives",

abstract = "The first examples of dimeric, di-PtII-containing heteropolytungstates are reported. The two isomeric di-platinum(II)-containing 22-tungsto-2-phosphates [anti-PtII2(α-PW11O39)2]10- (1 a) and [syn-PtII2(α-PW11O39)2]10- (2 a) were synthesized in aqueous pH 3.5 medium using one-pot procedures. Polyanions 1 a and 2 a contain a core comprising two face-on PtO4 units, with a Pt⋯Pt distance of 2.9-3 {\AA}. Both polyanions were investigated by single-crystal XRD, IR, TGA, UV/Vis, 31P NMR, ESI-MS, CID-MS/MS, electrochemistry, and DFT. On the basis of DFT and electrochemistry, we demonstrated that the {Pt2II} moiety in 1 a and 2 a can undergo fully reversible two-electron oxidation to {Pt2III}, accompanied by formation of a single Pt-Pt bond. Hence we have discovered the novel subclass of PtIII-containing heteropolytungstates.",

author = "Zhengguo Lin and Izarova, {Natalya V.} and Aleksandar Kondinski and Xiaolin Xing and Ali Haider and Linyuan Fan and Nina Vankova and Thomas Heine and Bineta Keita and Jie Cao and Changwen Hu and Ulrich Kortz",

note = "Funding Information: U.K. acknowledges the German Science Foundation (DFG, KO- 2288/20-1), the COST Actions CM1203 (PoCheMoN) and CM1006 (EUFEN), and the Chinese Academy of Sciences President's International Fellowship Initiative (Grant No. 2015VMA041). N.V.I. thanks the DFG (IZ-60/1-1) for financial support. We kindly acknowledge Johnson Matthey Plc for a loan of PtII salts. J.C. and C.H. thank the National Natural Science Foundation of China (21371025, 21173021, 21373027), the 111 Project (B07012), and 973 Program (2014CB932103). We acknowledge Dr. Maria Barsukova-Stuckart for some assistance with lab work. Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2016",

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doi = "10.1002/chem.201600555",

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TY - JOUR

T1 - Platinum-Containing Polyoxometalates

T2 - Syn- and anti-[PtII2(α-PW11O39)2]10- and Formation of the Metal-Metal-Bonded di-PtIII Derivatives

AU - Lin, Zhengguo

AU - Izarova, Natalya V.

AU - Kondinski, Aleksandar

AU - Xing, Xiaolin

AU - Haider, Ali

AU - Fan, Linyuan

AU - Vankova, Nina

AU - Heine, Thomas

AU - Keita, Bineta

AU - Cao, Jie

AU - Hu, Changwen

AU - Kortz, Ulrich

N1 - Funding Information: U.K. acknowledges the German Science Foundation (DFG, KO- 2288/20-1), the COST Actions CM1203 (PoCheMoN) and CM1006 (EUFEN), and the Chinese Academy of Sciences President's International Fellowship Initiative (Grant No. 2015VMA041). N.V.I. thanks the DFG (IZ-60/1-1) for financial support. We kindly acknowledge Johnson Matthey Plc for a loan of PtII salts. J.C. and C.H. thank the National Natural Science Foundation of China (21371025, 21173021, 21373027), the 111 Project (B07012), and 973 Program (2014CB932103). We acknowledge Dr. Maria Barsukova-Stuckart for some assistance with lab work. Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PY - 2016/4/11

Y1 - 2016/4/11

N2 - The first examples of dimeric, di-PtII-containing heteropolytungstates are reported. The two isomeric di-platinum(II)-containing 22-tungsto-2-phosphates [anti-PtII2(α-PW11O39)2]10- (1 a) and [syn-PtII2(α-PW11O39)2]10- (2 a) were synthesized in aqueous pH 3.5 medium using one-pot procedures. Polyanions 1 a and 2 a contain a core comprising two face-on PtO4 units, with a Pt⋯Pt distance of 2.9-3 Å. Both polyanions were investigated by single-crystal XRD, IR, TGA, UV/Vis, 31P NMR, ESI-MS, CID-MS/MS, electrochemistry, and DFT. On the basis of DFT and electrochemistry, we demonstrated that the {Pt2II} moiety in 1 a and 2 a can undergo fully reversible two-electron oxidation to {Pt2III}, accompanied by formation of a single Pt-Pt bond. Hence we have discovered the novel subclass of PtIII-containing heteropolytungstates.

AB - The first examples of dimeric, di-PtII-containing heteropolytungstates are reported. The two isomeric di-platinum(II)-containing 22-tungsto-2-phosphates [anti-PtII2(α-PW11O39)2]10- (1 a) and [syn-PtII2(α-PW11O39)2]10- (2 a) were synthesized in aqueous pH 3.5 medium using one-pot procedures. Polyanions 1 a and 2 a contain a core comprising two face-on PtO4 units, with a Pt⋯Pt distance of 2.9-3 Å. Both polyanions were investigated by single-crystal XRD, IR, TGA, UV/Vis, 31P NMR, ESI-MS, CID-MS/MS, electrochemistry, and DFT. On the basis of DFT and electrochemistry, we demonstrated that the {Pt2II} moiety in 1 a and 2 a can undergo fully reversible two-electron oxidation to {Pt2III}, accompanied by formation of a single Pt-Pt bond. Hence we have discovered the novel subclass of PtIII-containing heteropolytungstates.

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