A synthetic route to alkyl-pt(III) dinuclear complexes from olefins and its implication on the olefin oxidation catalyzed by amidate-bridged pt(III) dinuclear complexes

Kazuko Matsumoto, Yuji Nagai, Jun Matsunami, Kazuhiro Mizuno, Takeya Abe, Ryosuke Somazawa, Jun Kinoshita, Hideo Shimura

研究成果: Article

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抄録

Amidate-bridged Pt(III) dinuclear complexes [Pt2(NH3)4(Am)2(H2O)2]4+ (Am = amidate ligand) catalyze oxidation of olefins in acidic aqueous solution. Linear olefins are oxidized to ketones, whereas cyclic olefins are oxidized to epoxides. GC-MS analysis of the oxidation products obtained from the reaction in H2 18O showed that the oxygen atoms in the products are exclusively from water, suggesting that the reaction mechanism is basically similar to that of the Wacker reaction. In accordance with this mechanism, pivalamidate-bridged Pt(III) complex [Pt(III)2(NH3)4((CH3)3CCONH)2(H2O)2]4+ has been found to react with olefins to give alkyl complexes. Reactions with 4-penten-1-ol and ethylene glycol vinyl ether in acidic aqueous solution gave [Pt(III)2(NH3)4((CH3)3CCONH)2(CH2CH(CH2)3O)](NO3)3·H2O (7) and [Pt(III)2(NH3)4((CH3)3CCONH)2(CH2CHO)]- (NO3)3·H2O (9), respectively. The two compounds have been structurally confirmed by X-ray diffraction analysis and 1H, 13C, and 195Pt NMR spectroscopy. The 1H NMR of 9 shows that both π- and σ-complexes exist in equilibrium in D2O, although the X-ray structure is close to the σ-complex. High electrophilicity of the σ-carbon atoms of the compounds has been shown in the reactions with OH-. The above reactions with olefins can be a general route to prepare dimeric Pt(III)-alkyl complexes.

元の言語English
ページ(範囲)2900-2907
ページ数8
ジャーナルJournal of the American Chemical Society
120
発行部数12
DOI
出版物ステータスPublished - 1998 4 1

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Alkenes
Olefins
Oxidation
Cycloparaffins
Atoms
Ethylene Glycol
Epoxy Compounds
Ketones
X-Ray Diffraction
X ray diffraction analysis
Nuclear magnetic resonance spectroscopy
Ethylene glycol
Magnetic Resonance Spectroscopy
Carbon
Nuclear magnetic resonance
X-Rays
Oxygen
Ligands
Ethers
X rays

ASJC Scopus subject areas

  • Chemistry(all)

これを引用

A synthetic route to alkyl-pt(III) dinuclear complexes from olefins and its implication on the olefin oxidation catalyzed by amidate-bridged pt(III) dinuclear complexes. / Matsumoto, Kazuko; Nagai, Yuji; Matsunami, Jun; Mizuno, Kazuhiro; Abe, Takeya; Somazawa, Ryosuke; Kinoshita, Jun; Shimura, Hideo.

:: Journal of the American Chemical Society, 巻 120, 番号 12, 01.04.1998, p. 2900-2907.

研究成果: Article

Matsumoto, Kazuko ; Nagai, Yuji ; Matsunami, Jun ; Mizuno, Kazuhiro ; Abe, Takeya ; Somazawa, Ryosuke ; Kinoshita, Jun ; Shimura, Hideo. / A synthetic route to alkyl-pt(III) dinuclear complexes from olefins and its implication on the olefin oxidation catalyzed by amidate-bridged pt(III) dinuclear complexes. :: Journal of the American Chemical Society. 1998 ; 巻 120, 番号 12. pp. 2900-2907.
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abstract = "Amidate-bridged Pt(III) dinuclear complexes [Pt2(NH3)4(Am)2(H2O)2]4+ (Am = amidate ligand) catalyze oxidation of olefins in acidic aqueous solution. Linear olefins are oxidized to ketones, whereas cyclic olefins are oxidized to epoxides. GC-MS analysis of the oxidation products obtained from the reaction in H2 18O showed that the oxygen atoms in the products are exclusively from water, suggesting that the reaction mechanism is basically similar to that of the Wacker reaction. In accordance with this mechanism, pivalamidate-bridged Pt(III) complex [Pt(III)2(NH3)4((CH3)3CCONH)2(H2O)2]4+ has been found to react with olefins to give alkyl complexes. Reactions with 4-penten-1-ol and ethylene glycol vinyl ether in acidic aqueous solution gave [Pt(III)2(NH3)4((CH3)3CCONH)2(CH2CH(CH2)3O)](NO3)3·H2O (7) and [Pt(III)2(NH3)4((CH3)3CCONH)2(CH2CHO)]- (NO3)3·H2O (9), respectively. The two compounds have been structurally confirmed by X-ray diffraction analysis and 1H, 13C, and 195Pt NMR spectroscopy. The 1H NMR of 9 shows that both π- and σ-complexes exist in equilibrium in D2O, although the X-ray structure is close to the σ-complex. High electrophilicity of the σ-carbon atoms of the compounds has been shown in the reactions with OH-. The above reactions with olefins can be a general route to prepare dimeric Pt(III)-alkyl complexes.",
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T1 - A synthetic route to alkyl-pt(III) dinuclear complexes from olefins and its implication on the olefin oxidation catalyzed by amidate-bridged pt(III) dinuclear complexes

AU - Matsumoto, Kazuko

AU - Nagai, Yuji

AU - Matsunami, Jun

AU - Mizuno, Kazuhiro

AU - Abe, Takeya

AU - Somazawa, Ryosuke

AU - Kinoshita, Jun

AU - Shimura, Hideo

PY - 1998/4/1

Y1 - 1998/4/1

N2 - Amidate-bridged Pt(III) dinuclear complexes [Pt2(NH3)4(Am)2(H2O)2]4+ (Am = amidate ligand) catalyze oxidation of olefins in acidic aqueous solution. Linear olefins are oxidized to ketones, whereas cyclic olefins are oxidized to epoxides. GC-MS analysis of the oxidation products obtained from the reaction in H2 18O showed that the oxygen atoms in the products are exclusively from water, suggesting that the reaction mechanism is basically similar to that of the Wacker reaction. In accordance with this mechanism, pivalamidate-bridged Pt(III) complex [Pt(III)2(NH3)4((CH3)3CCONH)2(H2O)2]4+ has been found to react with olefins to give alkyl complexes. Reactions with 4-penten-1-ol and ethylene glycol vinyl ether in acidic aqueous solution gave [Pt(III)2(NH3)4((CH3)3CCONH)2(CH2CH(CH2)3O)](NO3)3·H2O (7) and [Pt(III)2(NH3)4((CH3)3CCONH)2(CH2CHO)]- (NO3)3·H2O (9), respectively. The two compounds have been structurally confirmed by X-ray diffraction analysis and 1H, 13C, and 195Pt NMR spectroscopy. The 1H NMR of 9 shows that both π- and σ-complexes exist in equilibrium in D2O, although the X-ray structure is close to the σ-complex. High electrophilicity of the σ-carbon atoms of the compounds has been shown in the reactions with OH-. The above reactions with olefins can be a general route to prepare dimeric Pt(III)-alkyl complexes.

AB - Amidate-bridged Pt(III) dinuclear complexes [Pt2(NH3)4(Am)2(H2O)2]4+ (Am = amidate ligand) catalyze oxidation of olefins in acidic aqueous solution. Linear olefins are oxidized to ketones, whereas cyclic olefins are oxidized to epoxides. GC-MS analysis of the oxidation products obtained from the reaction in H2 18O showed that the oxygen atoms in the products are exclusively from water, suggesting that the reaction mechanism is basically similar to that of the Wacker reaction. In accordance with this mechanism, pivalamidate-bridged Pt(III) complex [Pt(III)2(NH3)4((CH3)3CCONH)2(H2O)2]4+ has been found to react with olefins to give alkyl complexes. Reactions with 4-penten-1-ol and ethylene glycol vinyl ether in acidic aqueous solution gave [Pt(III)2(NH3)4((CH3)3CCONH)2(CH2CH(CH2)3O)](NO3)3·H2O (7) and [Pt(III)2(NH3)4((CH3)3CCONH)2(CH2CHO)]- (NO3)3·H2O (9), respectively. The two compounds have been structurally confirmed by X-ray diffraction analysis and 1H, 13C, and 195Pt NMR spectroscopy. The 1H NMR of 9 shows that both π- and σ-complexes exist in equilibrium in D2O, although the X-ray structure is close to the σ-complex. High electrophilicity of the σ-carbon atoms of the compounds has been shown in the reactions with OH-. The above reactions with olefins can be a general route to prepare dimeric Pt(III)-alkyl complexes.

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