Tetrakis triphenylphosphine platinum

Triphenylphosphine (15.4 g, 0.0588 mol) is dissolved in 200 mL of absolute ethanol at 65°. When the solution is clear, a solution of 1.4 g of potassium hydroxide in a mixture of 32 mL of ethanol and 8 mL of water is added. Then 5.24 g (0.0126 mol) of potassium tetrachloroplatinate(II) dissolved in 50 mL of water (0.0126 mol) is slowly added to the alkaline triphenylphosphine solution while stirring at 65°. The addition should be completed in about 20 min. A pale yellow compound begins to separate within a few minutes of the first addition. After cooling, the compound is recovered by filtration, washed with 150 mL of warm ethanol, then with 60 mL of cold water, and again with 50 mL of cold ethanol. The resulting pale yellow powder is dried in vacuo for 2 h. Yield 12.4 g, 79%. The compound must be stored under pure nitrogen. 

Tetrakis(triphenylphosphine)platinum(0) is a pale yellow powder that decomposes in the air to a red liquid at 118-120° and melts in vacuo (1 mm) to a yellow liquid at 159-160°. The infrared spectrum in Nujol shows absorption maxima at 700 (vs), 737 (vs), 837 (w), 992 (s), 1022 (s), 1077 (vs), 1147 (m), 1162 (m), 1302 (w), and 1432 (vs) cm L The compound is soluble in benzene with dissociation by leaving the benzene solution in the air, a white powder [the carbonatobis(triphenylphosphine)platinum(II) formed by action of oxygen and carbon dioxide] separates slowly. The compound reacts with carbon tetrachloride, giving ds-dichlorobis(triphenylphosphine)platinum(II).  

Tetrakis(triphenylphosphine)platinuin(0) (5.8 g, 0.00467 mol) is suspended in 250 mL of absolute ethanol under a nitrogen atmosphere and boiled, with stirring, for 2 h. The hot suspension is filtered, and the precipitate is washed with 30 mL of cold ethanol. The resulting yellow crystals are dried in vacuo for 2 h. Yield 3.0 g, 66%. The compound must be stored under pure nitrogen. 

Submitted by R. UGO, F. CARI.4TI, and G. LA MONICA Checked by JOSEPH J. MROWCAf 

Tris- and tetrakis(triphenylphosphine) derivatives of zerovalent platinum can be obtained by reduction of platinum(II) tri-phenylphosphine compounds by alcoholic potassium hydroxide or hydrazine. 1 The tris(triphenylphosphine) derivative is easily obtained from the tetrakis derivative by treatment with hot ethanol, t 

Tris- and tetrakis (triphenylphosphine) platinum (0) are the source of many platinum compounds. They react with carbon monoxide, acids/ methyl iodide/ fluoroalkyl derivatives/ carbon disulfide/ oxygen/ chloro/ fluoro/ and activated olefins/ hydrogen sulfide and selenide/ and sulfur dioxide/ yielding many platinum (II) or platinum (0) compounds which cannot be obtained easily by other routes. 

Triphenylphosphine (15.4 g., 0.0588 mole) is dissolved in 200 ml. of absolute ethanol at 65°. When the solution is clear, 

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Tetrakis(triphenylphosphine) platinum [14221-02-4] M 1244.3, m 118". Recrystd by adding hexane to a cold saturated solution in CgHg. It is soluble in C Hg and CHCI3 but insoluble in EtOH and hexane. A less pure product is obtained if crystd by adding hexane to a CHCI3 soln. Stable in air for several hours and completely stable under N2. [7 Am Chem Soc 2323 7958.J... 

A stoichiometric reaction of tetrakis(triphenylphosphine)platinum(0) with bis(pinacolato)diboron gives cis-diborylplatinum(n) complex in high yield (Scheme 3).38 The diborylplatinum complex then reacts with an alkyne, giving m-diboration product.40,41 These results indicate that the diboration proceeds through the general mechanism shown in Scheme 1 (E1 = E2 = Bpin), which involves the formation of diborylplatinum(n), insertion of an alkyne into the B-Pt bond, and reductive elimination. 

Platinum tetrakis(triphenylphosphine) see tetrakis(triphenylphosphine) platinum. 

Interaction of tetrakis(triphenylphosphine)platinum with elemental selenium leads to compound [Pt(Se2CH2)(PPh3)2] 91 in 93% yield (Equation 22) <1995HAC519>. 

A solution of tetrakis(triphenylphosphine)platinum (1.24 g., 0.001 mole) [Inorganic Syntheses, 11, 105 (1968)] in benzene (10 ml.) is added to a solution of triphenyl phosphite (1.55 g., 0.005 mole) in benzene (5 ml.). The resultant pale-colored solution is filtered, diluted with n-hexane (25 ml.), and cooled overnight at 5°. The white crystalline product is filtered off, extracted with warm n-hexane (25 ml.) to remove coprecipitated tri-phenylphosphine, and dried in vacuo. Yield is 1.2 g. (84%). The product may be further purified by dissolving in the minimum volume of benzene and reprecipitating by addition of n-hexane (m.p. 148-154°). Anal. Calcd. for C72H60Oi2P4Pt ... 

Carbon dioxide and oxygen are bubbled through a solution of 5 g of tetrakis-(triphenylphosphine)platinum, Pt [P(CgH5)3] 4, (4 mmole) in 120 mL of benzene. After 30 minutes the mixture is very pale yellow. The solid is recovered using a medium-porosity filter and is washed with benzene (50 mL). The crude product (3-3.5 g) is a mixture of the carbonato and peroxycarbonato complexes. To complete the conversion to the carbonato complex, the crude product is dissolved in 75 mL of dichloromethane, and 5 g (19 mmole) of triphenylphos-phine is added. The mixture is refluxed overnight. Benzene (75 mL) is added to the mixture and the volume is reduced by half on a rotary evaporator. The colorless solid is recovered using a medium-porosity filter, washed with benzene (50 mL) and diethyl ether (25 mL), and then dried in vacuo. The yield is 2.5 g (73%). Anal, (as benzene solvate) Calcd. for PtC43H36P203 C, 60.2 H, 4.2. Found C 59.6 H, 4.1. 

Tetrakis(triphenylphosphine) platinum [14221-02-4] M 1244.3, m 118 . It forms yellow crystals on adding hexane to a cold saturated solution in C6H6- It is soluble in and CHCI3 but... 

Reaction of [l,2,3]selenadiazole 281 with tetrakis(triphenylphosphine)platinum leads to the formation of a novel selenoplatinum catalyst 283 <05TL1001>. This complex has been used as a catalyst for the hydrosilylation of terminal alkynes. Both 3,3-dimethylbut-l-yne and trimethylsilylacetylene undergo regioselective and sterereoselective hydrosilylation with dimethylphenylsilane in the presence of 0.0002 mol% of 283 to afford (E)-285 in good yields. In the case of phenylacetylene, the hydrosilylation is regioselective however, the stereoselectivity is reduced to 5 1 (E Z). 

Tetrakis(triphenylphosphine)platinum and fluoroalkanecarboxylic acids form the ionic complexes [(PhsP)3PtH](OisCRF),H (Rf = CF, CgF,... 

In experiments aimed at the preparation of stable benzyne complexes of platinum of type (51), 1,2,3-benzothiadiazole 1,1-dioxides (52 R=H or Me), which are known to fragment under mild conditions, were used as a potential source of benzyne. However, their interaction with tetrakis-(triphenylphosphine)platinum in benzene did not giye the required benzyne complexes, but resulted in excellent yields of yellow crystalline azocomplexes of structure (53) or possibly (54 R = H or Me). ... 

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