Tris triphenylphosphine platinum

Tetrakis(triphenylphosphine)platinum(0) (5.8 g., 0.00467 mole) is suspended in 250 ml. of absolute ethanol under a nitrogen atmosphere and boiled, with stirring, for 2 hours. 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 hours. Yield, 3.0 g., 66%. The compound must be stored under pure nitrogen. Anal. Calcd. for C64H45P3Pt C, 66.0 H, 4.59 P, 9.48. Found C, 65.90 H, 4.69 P, 9.55. 

The compound dissolves in benzene, with dissociation. By leaving the benzene solution in the air, carbonatobis (triphenyl-phosphine) platinum(II) separates slowdy. It reacts easily with carbon tetrachloride giving cfs-dichlorobis(triphenylphos-phine)platinum(II). The complex is tricoordinated in the solid state, and shows a nearly pure hybridization of the platinum atom.  

Cook and G. S. Janhal, Inorg. N zicl, Chem. Letters, 3, 31 (1967), and references therein. 

SQUARE PLANAR DICHLOROPALLADIUM (II) COMPLEXES WITH ORGANOPHOSPHORUS LIGANDS 

Submitted by J. M. JENKINS and J. G. VERKADE Checked by JOHN GODDARDt and FRED BASOLOf 

Moielli, A. Segre, R. Ugo, G. La Monica, S. Cenini, F. Conti, and F. Bonati, Cheat. Conunun., 524 (1967X 

Li2CgHg + [Pta2(CgHi2)] + 3C7Hio [Pt(C7Hio)3]+ 2LiCl 

Dichloro(l,5-cyclooctadiene)platinum(II) may be prepared from hexa-chloroplatinic acid, or by heating bis(benzonitrile)dichloroplatinum(II) in 1,5-cyclooctadiene at 14S°C for 5 min, or from potassium tetra-chloroplatinate(2-). The complex [PtCl2(CgHi2)] has a very low solubility in the reaction mixture and must be finely ground to ensure complete reaction. The olefins 1,5-cyclooctadiene, bicyclo[2.2.1]hept-2-ene(2-norbomeneX and 1,3,5,7-cyclooctatetraene and all solvents should be dried and freshly distilled under nitrogen. In particular, peroxide-free diethyl ether is first dried over sodium wire and then distilled under nitrogen from sodium-benzophenone. 

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A complex of homoadamantyne (273) has been prepared by dehalogena-tion of 272 in the presence of tris(triphenylphosphine)platinum(0) [Eq. (43)]." Trapping free homoadamantyne was presumed to be the mechanism of this reaction. However, reduction of neither an initially formed 77-com-plex2,82 nor a C-Br insertion product93 was excluded. Interestingly, the free alkyne, generated by dehydrohalogenation of the vinyl bromide, was successfully trapped with diphenyl-wo-benzofuran. 

Pt(0) complexes 343, 344, and 345, all of which have allene ground states, were prepared as illustrated and in Scheme 43 for 343 by treating appropriate bromocycloheptatrienes with KOr-Bu in the presence of tris (triphenylphosphine)platinum(O). The mechanism of this reaction is in ques-... 

Many catalysts, certainly those most widely used such as platinum, palladium, rhodium, ruthenium, nickel, Raney nickel, and catalysts for homogeneous hydrogenation such as tris(triphenylphosphine)rhodium chloride are now commercially available. Procedures for the preparation of catalysts are therefore described in detail only in the cases of the less common ones (p. 205). Guidelines for use and dosage of catalysts are given in Table 1. 

In the absence of triphenylphosphine a tris-SPO platinum complex forms when SPO is reacted with Pt(cod)2, which is insoluble and for which the structure is not known it could be either a hydride (4) or an oligomeric or a dimeric S PO complex (5) lacking one molecule of hydrogen. The reaction with alkene, CO and H2 gives complex 6, which was identified as the acyl tris-SPO complex by NMR. It shows an... 

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 ... 

Enones are reduced to saturated ketones by catalytic hydrogenation provided the reaction is stopped following the absorption of 1 mol of hydrogen. " A number of catalysts were found useful for this, including platinum, platinum oxide,Pt/C, " Pd/C, - Rh/C, " tris(triphenylphosphine)rhodium chloride, - nickel-aluminum alloy in 10% aqueous NaOH, and zinc-reduced nickel in an aqueous medium. Mesityl oxide is formed from acetone and reduced in a single pot to methyl isobutyl ketone using a bifunctional catalyst which comprised palladium and zirconium phosphate (Scheme 20). 

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. 

Hydrogenation Copper chromite (Lazier catalyst). Copper chromium oxide (Adkins catalyst). Lindlar catalyst (see also Lithium ethoxyacetylide, Malealdehyde, Nickel boride). Nickel catalysts. Palladium catalysts. Palladium hydroxide on carbon. Perchloric acid (promoter). Platinum catalysts. Raney catalysts, Rhenium catalysts. Rhodium catalysts. Stannous chloride. Tributylborane. Trifluoroicetic acid, Tris (triphenylphosphine)chlororhodium. 

SClFjOjPtCijHjo, Platinum(II), chloro-bis(triethylphosphine)(trifluoro-methanesulfonato)-, cis-, 26 126, 28 27 SClNOjPCijHij, Sulfamoyl chloride, (tri-phenylphosphoranylidene)-, 29 27 SCI2OSP3C55H4S, Osmium(II), dichloro(thio-carbonyl)tris(triphenylphosphine)-, 26 185... 

Tetrachloropalladate(II) ion catalyzes the interconversion of 1- and 2-butenes in aqueous solutions containing chloride and hydronium ions. Sodium tetrachloropalladate(II) catalyzes the conversion of allylbenzene to propenyl-benzene in acetic acid solutions. Tetrakis(ethylene))Lt,/x -dichlororhodium(l) catalyzes butene isomerization in methanolic hydrogen chloride solutions . Cyclooctadienes isomerize in benzene-methanol solutions of dichlorobis-(triphenylphosphine)platinum(11) and stannous chloride. Chloroplatinic acid-stannous chloride catalyzes the isomerization of pentenes. Coordination complexes of zero-valent nickel with tris(2-biphenylyl)phosphite or triphenyl-phosphine catalyze the isomerization of cis-1,2-divinylcyclobutane to a mixture of c/5,m-l, 5-cyclooctadiene and 4-vinylcyclohexene . Detailed discussions of reaction kinetics and mechanisms appear in the papers cited. 

Materials. The ultraviolet initiator Darocur 1173 (2-hydroxy-2-methyl-l-phenyl-propan-1-one) was purchased from EM Science and was used as received. Dimethylacrylamide (DMA), methacryloyl chloride (MC), allyloxytrimethylsilane and (tris(triphenylphosphine)rhodium)chloride were purchased from Aldrich Chemical Co. DMA and MC were distilled under nitrogen prior to use. 1,3-Tetramethyldisiloxane, methacryloylpropyltrichlorosilane, and 1,3-tetramethyldisiloxane platinum complex (2 % platinum in xylenes) were purchased from Gelest, The fluorinated allylic ether, allyloxy octafluoropentane, was prepared by the phase transfer catalyzed reaction of allyl bromide with octafluoropentanol using tetrabutylammonium hydrogen sulfate, tetrahydrofuran and 50% (w/w) NaOH (11). The fluorinated side-chain methacrylate end-capped siloxane (FSi) was prepared according to a literature procedure. All other solvents and reagents were used as received. 

C4 2H3 60i,P2Pt, o-(Diphenylphosphino)phenyl-cis-1,2-dicarbomethoxy-ethenyltriphenylphosphineplatinum, 44B, 1137 C42H3s02P2Pt, 1-Oxo-2-oxa-3,3-dimethylpent-4-ene-l,4-diylbis(tri-phenylphosphine)platinum(II), 42B, 645 Cfl 2Hfl oOiiP2Pt f trans-Bis(ethoxycarbonyl)bis (triphenylphosphine)platinum, 40B, 719... 

CflflH36Cl5lrN20P2, Dichloro-(4-methoxyphenyldiimide-C(2),N )bis(tri-phenylphosphine)iridium chloroform solvate, 40B, 722 CflflHa60aP2Pt2, M (Dimethyl acetylenedicarboxylate)bis[carbonyl(triphenylphosphine )platinum( I )](Pt-Pt), 46B, 1291 C4 flH3 yBrP2Pt, trans-Bromo-(trans-styryl)bis(triphenylphosphine)plat-... 

C51H5 lOjPPd, (1-T -1,2,3,4-Tetra(p-tolyl)-4-phenyl-1, 3-butadienyD-(acetylacetonato)(dimethylphenylphosphine)palladium, 44B, 735 C5iHs506P2Pd2f M (Cyclopentadienyl)-M (2-methylallyl)-bis(tri-o-tolylphosphite P)-dipalladium(Pd-Pd), 43B, 1026 Cs2HijoP2Pt, ciS Bis(phenylacetylido)bis(triphenylphosphine)platinum-(II), 43B, 1030... 

Cg (jH(j g02P3PtS 0.7 SO2, Tris(triphenylphosphine) (sulfur dioxide)-platinum sulfur dioxide solvate, 42B, 994 CgftHftgClIrNOgPa, Hydridonitrosyltris(triphenylphosphine)iridiumd) perchlorate (brown isomer), 40B, 1062 CgftHftgClIrNOgPa, Hydridonitrosyltris(triphenylphosphine)iridiumd) perchlorate (black isomer), 37B, 667 CgftHft6CoN2P3 f Hydridodinitrogentrisdriphenylphosphine)cobalt(I), 34B, 618 40B, 1132... 

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