Activation of water molecule. 2. Generation of strong hydroxo bases by the reaction of water with platinum(0) phosphine complexes and the applications as catalysts for hydrogen-deuterium exchange and hydration reactions

Yoshida, Tomohiro; Matsuda, Tomonori; Okano, Tamon; Kitani, Tetsumi; Otsuka, Sei

doi:10.1021/ja00502a017

Cited by 133 publications

(49 citation statements)

References 15 publications

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“…Organoplatinum(II) hydroxo complexes have long been studied and were reported to exhibit a nucleophilic character [46,47] in a similar way to the more common alkoxoplatinum(II) complexes [48][49][50][51][52][53]. The hydroxo platinum complexes show a tendency to form dinuclear complex by bridging of the OH ligand [54][55][56][57][58][59][60].…”

Section: Transmetalation Of Hydroxoplatinum Complexesmentioning

confidence: 99%

Transmetalation of arylpalladium and platinum complexes. Mechanism and factors to control the reaction

Suzaki

Yagyu

Osakada

2007

Journal of Organometallic Chemistry

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Section: Transmetalation Of Hydroxoplatinum Complexesmentioning

confidence: 99%

Transmetalation of arylpalladium and platinum complexes. Mechanism and factors to control the reaction

Suzaki

Yagyu

Osakada

2007

Journal of Organometallic Chemistry

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“…It is most easily explained by exchange ofsurface platinum hydrides (as protons) with protons in the solvent. This type of exchange is also rapid for d8-transition metal hydrides in homogeneous solution (18,19).…”

Section: Discussionmentioning

confidence: 90%

Heterogeneous platinum-catalyzed hydrogenation of dialkyl(diolefin)platinum(II) complexes: A new route to platinum surface alkyls

McCarthy

Shih²,

Whitesides³

1981

Proc. Natl. Acad. Sci. U.S.A.

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Platinum metal catalyzes the reduction of dialkyl(diolefin)platinum(H) complexes by dihydrogen to alkanes and platinum (O). The reaction involves adsorption of the platinum(II) complex on the platinum(O) catalyst surface with conversion of the alkyl moieties to platinum surface alkyls; these appear as alkane products. The platinum atom originally present in the soluble organoplatinum species becomes part of the platinum(O) surface.Platinum surface alkyls are believed to be intermediates in platinum-catalyzed heterogeneous reactions ofhydrocarbons (1-8).Among the difficulties encountered in studying the mechanisms of these reactions is that of establishing simultaneously the structure and reactivity of the intermediates. The application of surface spectroscopy to problems in catalysis is beginning to yield valuable structural information concerning surface alkyls under certain conditions, and studies of product distributions, especially using isotopically labeled reactants, have established mechanistically informative patterns of reactivity for (usually) different alkyls under different conditions (9)(10)(11)(12). Nonetheless, in no instance are both the structure and the characteristic reactivity of a platinum surface alkyl known, particularly under the conditions prevailing during use of a heterogeneous platinum catalyst in synthesis. DISCUSSIONHere we describe experiments in which the platinum-catalyzed heterogeneous hydrogenation of soluble dialkyl(diolefin) platinum(II) complexes (olefin2PtR2) was examined (Eq. 1).We propose, on the basis of these experiments, that this reaction involves adsorption of the dialkylplatinum(II) moiety at the platinum surface; it thus provides the basis for a new method ofgenerating platinum surface alkyls. In this method, the initial structure of the organic portion of the surface alkyl is well defined, and these surface species are generated on a working platinum catalyst. The method is thus complementary to techniques used previously in examining heterogeneous reactions catalyzed by platinum and provides a new point of entry into catalytic cycles occurring on platinum.The reaction of dialkyl(diolefin)platinum(II) complexes in hydrocarbon solution at ambient temperature with dihydrogen (1-3 atm; 1 atm = 1.013 X 105 Pa) in the presence of porous glass beads coated with platinum(0) rapidly and quantitatively yields the alkanes derived by hydrogenolysis of the PtR2 group and hydrogenation ofthe diolefin. No alkyl dimers are formed. The platinum originally present in the soluble organoplatinum compound is deposited on the surface of the platinum catalyst and becomes the catalytic surface for subsequent reduction. The addition of small quantities of thiophene or triphenylphosphine (0.5 mol %, based on olefin2PtR2) blocks the reduction in a solution containing previously active catalyst; these poisoned catalysts are also inactive for the hydrogenation of cyclohexene.Kinetic information concerning the reaction was obtained by carrying out reductions using a preformed active ...

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“…2 Re 2 (CO) 10 (6.13) In 1979, the first isolation of the hydrido(hydroxo) complex by oxidative addition of water to an electron-rich platinum(0) complex was accomplished by Yoshida and Otsuka [22]. Highly coordinatively unsaturated bis(triisopropylphosphine)platinum (24b) can activate water very easily at room temperature to give the hydrido(hydroxo) complex, trans-[PtH(OH)(P i Pr 3 ) 2 ] (25), as an extremely air-sensitive and thermally unstable colorless compound (Scheme 6-2).…”

Section: Complexes Resulting From Activation Of Water: Hydrido(hydroxmentioning

confidence: 99%

“…Some Pt complexes bearing electron-donating phosphines can also catalyze the hydration of the C=C double bond of acrylonitrile or crotonitrile and yielded β-hydroxypropionitrile or β-hydroxybutyronitrile respectively besides the corresponding amide (Eq. 6.38) [22,75]. Among the platinum phosphine complexes examined, [Pt(PEt 3 ) 3 ] (26a), carrying less bulky ligands, was the most effective for the hydration of the olefinic bond.…”

Section: Hydration and Methanolysis Of Nitrilementioning

confidence: 99%

“…Hydrido ( peralkylphosphine complexes such as [PtL 3 ] (26) (a: L = PEt 3 , b: L = P i Pr 3 ), and [Pt(PCy 3 ) 2 ] (24b) can catalyze H-D exchange of activated C-H bonds such as α-hydrogen atoms of ketones, aldehydes, sulfones, sulfoxides, and nitroalkanes with D 2 O [22]. For example, 86% of the methyl hydrogens of acetophenone were exchanged for deuterium by heating with a large excess of D 2 O in the presence of a catalytic amount of [Pt(P i Pr 3 ) 3 ] (26b) at 80°C for 20 h in THF.…”

Section: H-d Exchange Reactionmentioning

confidence: 99%

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O–H Activation and Addition to Unsaturated Systems

Tani

Kataoka

2001

Catalytic Heterofunctionalization

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Activation of water molecule. 2. Generation of strong hydroxo bases by the reaction of water with platinum(0) phosphine complexes and the applications as catalysts for hydrogen-deuterium exchange and hydration reactions

Cited by 133 publications

References 15 publications

Transmetalation of arylpalladium and platinum complexes. Mechanism and factors to control the reaction

Transmetalation of arylpalladium and platinum complexes. Mechanism and factors to control the reaction

Heterogeneous platinum-catalyzed hydrogenation of dialkyl(diolefin)platinum(II) complexes: A new route to platinum surface alkyls

O–H Activation and Addition to Unsaturated Systems

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