Polyoxometalate-Assisted, One-Pot Synthesis of a Pentakis[(triphenylphosphane)gold]ammonium(2+) Cation Containing Regular Trigonal-Bipyramidal Geometries of Five Bonds to Nitrogen
Novel intercluster compounds consisting of pentakis[(triphenylphosphane)gold]ammonium(2+) cation (1) and Keggin polyoxometalate (POM) anions, i.e., {[Au(PPh3)]5(μ5-N)}3[α-PM12O40]2 (1-PW for M = W; 1-PMo for M = Mo), were synthesized in 30-36% yield by one-pot reaction of the protonic acid form of the Keggin POMs, H3[α-PM12O40]·nH2O (n = 13 for M = W; n = 15 for M = Mo) with monomeric (triphenylphosphane)gold(I) carboxylate [Au(RS-pyrrld)(PPh3)] [RS-Hpyrrld = (RS)-2-pyrrolidone-5-carboxylic acid] in the presence of aqueous NH3 at a molar ratio of 2:15:x (x = 3 for 1-PW; x = 7.5 for 1-PMo). These compounds resulted from the nitrogen-centered phosphanegold(I) clusterization of in situ generated monomeric phosphanegold(I) units, [Au(PPh3)]+ or [Au(L)(PPh3)]+ (L = NH3 or solvent), during the carboxylate elimination of [Au(RS-pyrrld)(PPh3)] in the presence of the Keggin POMs and aqueous NH3. The products 1-PW and 1-PMo were characterized by elemental analysis, Fourier transform infrared, thermogravimetric and differential thermal analyses (TGA/DTA), X-ray crystallography, and solid-state cross-polarization magic-angle-spinning (CPMAS) (31P and 15N) and solution (31P{1H} and 1H) NMR spectroscopy. The lattice contained three independent {[Au(PPh3)]5(μ5-N)}2+ cations, of which two took regular trigonal-bipyramidal (TBP) geometries and the third took a distorted, square-pyramidal (SP) geometry. These geometries are in contrast to those reported by Schmidbaur's group for {[Au(PPh3)]5(μ5-N)}2+ cations as BF4 salts. Density functional theory and ONIOM calculations for {[(L3P)Au]nN}(n-3)+ (L = H or Ph; n = 4-6) showed that the pentacoordinate cluster is energetically most stable and its TBP structure is only 1.6 kcal mol-1 more stable than its SP structure, in accordance with the experimental facts.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2018 |
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| Erschienen: |
2018 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:57 |
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| Enthalten in: |
Inorganic chemistry - 57(2018), 3 vom: 05. Feb., Seite 1504-1516 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Nomiya, Kenji [VerfasserIn] |
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| Anmerkungen: |
Date Completed 07.03.2018 Date Revised 07.03.2018 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.inorgchem.7b02795 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM280301111 |
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| 100 | 1 | |a Nomiya, Kenji |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Polyoxometalate-Assisted, One-Pot Synthesis of a Pentakis[(triphenylphosphane)gold]ammonium(2+) Cation Containing Regular Trigonal-Bipyramidal Geometries of Five Bonds to Nitrogen |
| 264 | 1 | |c 2018 | |
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| 500 | |a Date Completed 07.03.2018 | ||
| 500 | |a Date Revised 07.03.2018 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Novel intercluster compounds consisting of pentakis[(triphenylphosphane)gold]ammonium(2+) cation (1) and Keggin polyoxometalate (POM) anions, i.e., {[Au(PPh3)]5(μ5-N)}3[α-PM12O40]2 (1-PW for M = W; 1-PMo for M = Mo), were synthesized in 30-36% yield by one-pot reaction of the protonic acid form of the Keggin POMs, H3[α-PM12O40]·nH2O (n = 13 for M = W; n = 15 for M = Mo) with monomeric (triphenylphosphane)gold(I) carboxylate [Au(RS-pyrrld)(PPh3)] [RS-Hpyrrld = (RS)-2-pyrrolidone-5-carboxylic acid] in the presence of aqueous NH3 at a molar ratio of 2:15:x (x = 3 for 1-PW; x = 7.5 for 1-PMo). These compounds resulted from the nitrogen-centered phosphanegold(I) clusterization of in situ generated monomeric phosphanegold(I) units, [Au(PPh3)]+ or [Au(L)(PPh3)]+ (L = NH3 or solvent), during the carboxylate elimination of [Au(RS-pyrrld)(PPh3)] in the presence of the Keggin POMs and aqueous NH3. The products 1-PW and 1-PMo were characterized by elemental analysis, Fourier transform infrared, thermogravimetric and differential thermal analyses (TGA/DTA), X-ray crystallography, and solid-state cross-polarization magic-angle-spinning (CPMAS) (31P and 15N) and solution (31P{1H} and 1H) NMR spectroscopy. The lattice contained three independent {[Au(PPh3)]5(μ5-N)}2+ cations, of which two took regular trigonal-bipyramidal (TBP) geometries and the third took a distorted, square-pyramidal (SP) geometry. These geometries are in contrast to those reported by Schmidbaur's group for {[Au(PPh3)]5(μ5-N)}2+ cations as BF4 salts. Density functional theory and ONIOM calculations for {[(L3P)Au]nN}(n-3)+ (L = H or Ph; n = 4-6) showed that the pentacoordinate cluster is energetically most stable and its TBP structure is only 1.6 kcal mol-1 more stable than its SP structure, in accordance with the experimental facts | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Endo, Kohei |e verfasserin |4 aut | |
| 700 | 1 | |a Murata, Yuichi |e verfasserin |4 aut | |
| 700 | 1 | |a Sato, Shinya |e verfasserin |4 aut | |
| 700 | 1 | |a Shimazaki, Sho |e verfasserin |4 aut | |
| 700 | 1 | |a Horie, Shogo |e verfasserin |4 aut | |
| 700 | 1 | |a Nagashima, Eri |e verfasserin |4 aut | |
| 700 | 1 | |a Yasuda, Yuta |e verfasserin |4 aut | |
| 700 | 1 | |a Yoshida, Takuya |e verfasserin |4 aut | |
| 700 | 1 | |a Matsunaga, Satoshi |e verfasserin |4 aut | |
| 700 | 1 | |a Matsubara, Toshiaki |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Inorganic chemistry |d 1966 |g 57(2018), 3 vom: 05. Feb., Seite 1504-1516 |w (DE-627)NLM110650298 |x 1520-510X |7 nnns |
| 773 | 1 | 8 | |g volume:57 |g year:2018 |g number:3 |g day:05 |g month:02 |g pages:1504-1516 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1021/acs.inorgchem.7b02795 |3 Volltext |
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