Isostructural Pd II and Pt II pyrophosphato complexes: Polymorphism and unusual bond character in d 8-d 8 systems

Nadia Marino, Christopher H. Fazen, James D. Blakemore, Christopher D. Incarvito, Nilay Hazari, Robert Patrick Doyle

Research output: Contribution to journalArticle

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Abstract

Isostructural, "clamshell"-like, neutral dimeric pyrophosphato complexes of general formula {[M(bipy)] 2(μ-P 2O 7)} [M = Pd II (1) or Pt II (2)] were synthesized and studied through single-crystal X-ray diffraction, IR, 31P NMR spectroscopy, and MALDI-TOF mass spectrometry. Compound 1 was synthesized through the reaction of palladium(II) acetate, 2,2′-bipyridine (bipy), and sodium pyrophosphate (Na 4P 2O 7) in water. Compound 2 was prepared through two different routes. The first involved the reaction of the Pt IV precursor Na 2PtCl 6, bipy, and Na 4P 2O 7 in water, followed by reduction in DMF. The second involved the reaction of the Pt II precursor K 2PtCl 4, bipy, and Na 4P 2O 7 in water. Both complexes crystallize in the monoclinic chiral space group Cc as hexahydrates, 1 · 6H 2O (1a, yellow crystals) and 2 · 6H 2O (2a, orange crystals), and exhibit a zigzag chain-like supramolecular packing arrangement with short and long intra/intermolecular metal-metal distances [3.0366(3)/4.5401(3) Å in 1a; 3.0522(3)/4.5609(3) Å in 2a]. A second crystalline phase of the Pt species was also isolated, with formula 2 · 3.5H 2O (2b, deep green crystals), characterized by a dimer-of-dimers (pseudo-tetramer) structural submotif. Green crystals of 2b could be irreversibly converted to the orange form 2a by exposure to air or water, without retention of crystallinity, while a partial, reversible crystal-to-crystal transformation occurred when 2a was dried in vacuo. 31P NMR spectra recorded for both 1 and 2 at various pHs revealed the occurrence of a fluxional protonated/deprotonated system in solution, which was interpreted as being composed, in the protonated form, of [HO=PO 3] + (P α) and O=PO 3 (P β) pyrophosphate subunits. Compounds 1 and 2 exhibited two successive one-electron oxidations, mostly irreversible in nature; however, a dependence upon pH was observed for 1, with oxidation only occurring in strongly basic conditions. Density functional theory and atoms in molecules analyses showed that a d 8-d 8 interaction was present in 1 and 2.

Original languageEnglish (US)
Pages (from-to)2507-2520
Number of pages14
JournalInorganic Chemistry
Volume50
Issue number6
DOIs
StatePublished - Mar 21 2011

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polymorphism
Polymorphism
Crystals
crystals
Water
Dimers
water
Metals
dimers
Oxidation
nuclear magnetic resonance
oxidation
metals
Nuclear magnetic resonance spectroscopy
Density functional theory
Mass spectrometry
palladium
acetates
Infrared spectroscopy
crystallinity

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

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Isostructural Pd II and Pt II pyrophosphato complexes : Polymorphism and unusual bond character in d 8-d 8 systems. / Marino, Nadia; Fazen, Christopher H.; Blakemore, James D.; Incarvito, Christopher D.; Hazari, Nilay; Doyle, Robert Patrick.

In: Inorganic Chemistry, Vol. 50, No. 6, 21.03.2011, p. 2507-2520.

Research output: Contribution to journalArticle

Marino, Nadia ; Fazen, Christopher H. ; Blakemore, James D. ; Incarvito, Christopher D. ; Hazari, Nilay ; Doyle, Robert Patrick. / Isostructural Pd II and Pt II pyrophosphato complexes : Polymorphism and unusual bond character in d 8-d 8 systems. In: Inorganic Chemistry. 2011 ; Vol. 50, No. 6. pp. 2507-2520.
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abstract = "Isostructural, {"}clamshell{"}-like, neutral dimeric pyrophosphato complexes of general formula {[M(bipy)] 2(μ-P 2O 7)} [M = Pd II (1) or Pt II (2)] were synthesized and studied through single-crystal X-ray diffraction, IR, 31P NMR spectroscopy, and MALDI-TOF mass spectrometry. Compound 1 was synthesized through the reaction of palladium(II) acetate, 2,2′-bipyridine (bipy), and sodium pyrophosphate (Na 4P 2O 7) in water. Compound 2 was prepared through two different routes. The first involved the reaction of the Pt IV precursor Na 2PtCl 6, bipy, and Na 4P 2O 7 in water, followed by reduction in DMF. The second involved the reaction of the Pt II precursor K 2PtCl 4, bipy, and Na 4P 2O 7 in water. Both complexes crystallize in the monoclinic chiral space group Cc as hexahydrates, 1 · 6H 2O (1a, yellow crystals) and 2 · 6H 2O (2a, orange crystals), and exhibit a zigzag chain-like supramolecular packing arrangement with short and long intra/intermolecular metal-metal distances [3.0366(3)/4.5401(3) {\AA} in 1a; 3.0522(3)/4.5609(3) {\AA} in 2a]. A second crystalline phase of the Pt species was also isolated, with formula 2 · 3.5H 2O (2b, deep green crystals), characterized by a dimer-of-dimers (pseudo-tetramer) structural submotif. Green crystals of 2b could be irreversibly converted to the orange form 2a by exposure to air or water, without retention of crystallinity, while a partial, reversible crystal-to-crystal transformation occurred when 2a was dried in vacuo. 31P NMR spectra recorded for both 1 and 2 at various pHs revealed the occurrence of a fluxional protonated/deprotonated system in solution, which was interpreted as being composed, in the protonated form, of [HO=PO 3] + (P α) and O=PO 3 (P β) pyrophosphate subunits. Compounds 1 and 2 exhibited two successive one-electron oxidations, mostly irreversible in nature; however, a dependence upon pH was observed for 1, with oxidation only occurring in strongly basic conditions. Density functional theory and atoms in molecules analyses showed that a d 8-d 8 interaction was present in 1 and 2.",
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T2 - Polymorphism and unusual bond character in d 8-d 8 systems

AU - Marino, Nadia

AU - Fazen, Christopher H.

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N2 - Isostructural, "clamshell"-like, neutral dimeric pyrophosphato complexes of general formula {[M(bipy)] 2(μ-P 2O 7)} [M = Pd II (1) or Pt II (2)] were synthesized and studied through single-crystal X-ray diffraction, IR, 31P NMR spectroscopy, and MALDI-TOF mass spectrometry. Compound 1 was synthesized through the reaction of palladium(II) acetate, 2,2′-bipyridine (bipy), and sodium pyrophosphate (Na 4P 2O 7) in water. Compound 2 was prepared through two different routes. The first involved the reaction of the Pt IV precursor Na 2PtCl 6, bipy, and Na 4P 2O 7 in water, followed by reduction in DMF. The second involved the reaction of the Pt II precursor K 2PtCl 4, bipy, and Na 4P 2O 7 in water. Both complexes crystallize in the monoclinic chiral space group Cc as hexahydrates, 1 · 6H 2O (1a, yellow crystals) and 2 · 6H 2O (2a, orange crystals), and exhibit a zigzag chain-like supramolecular packing arrangement with short and long intra/intermolecular metal-metal distances [3.0366(3)/4.5401(3) Å in 1a; 3.0522(3)/4.5609(3) Å in 2a]. A second crystalline phase of the Pt species was also isolated, with formula 2 · 3.5H 2O (2b, deep green crystals), characterized by a dimer-of-dimers (pseudo-tetramer) structural submotif. Green crystals of 2b could be irreversibly converted to the orange form 2a by exposure to air or water, without retention of crystallinity, while a partial, reversible crystal-to-crystal transformation occurred when 2a was dried in vacuo. 31P NMR spectra recorded for both 1 and 2 at various pHs revealed the occurrence of a fluxional protonated/deprotonated system in solution, which was interpreted as being composed, in the protonated form, of [HO=PO 3] + (P α) and O=PO 3 (P β) pyrophosphate subunits. Compounds 1 and 2 exhibited two successive one-electron oxidations, mostly irreversible in nature; however, a dependence upon pH was observed for 1, with oxidation only occurring in strongly basic conditions. Density functional theory and atoms in molecules analyses showed that a d 8-d 8 interaction was present in 1 and 2.

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