Platinum trans-, chloride

A Pt(II)-bridged wire compound was prepared by Mayor et al. [18] by treating trans-bis(triphenylphosphane)platinum(II) chloride (63) with the alkyne 4 and Cul as catalyst (Scheme 10.20). The trans configuration of the product 64 was confirmed by X-ray crystallographic analysis. 

Bis(4-imino-2-pentanonato)nickel(II), synthesis 60 Tetraamminepalladium(II) tetrachloropalladate(II) and trans-dichlorodiamminepalladium(II), synthesis 61 Tris(ethylenediamine)platinum(IV) chloride, synthesis 62 ct8-Dichloro(ethylenediamine)platinum(II), synthesis 63... 

PtClNPSejCagHzs, Platinum(II), chloro-(iV,N-diethyldiselenocarbamato)(tri-phenylphosphine)-, 21 10 PtCl2HgIN2Pt, Platinum(II), diamminechlo-roiodo-, trans-, chloride, 22 124... 

Both isomers respond to Kurnakov s test. In hot aqueous solution, the cis isomer reacts with saturated aqueous thiourea to give a bright yellow solution, from which yellow needles of tetrakis(thiourea)platinum(II) chloride deposit on cooling, while the trans isomer gives no visible reaction, but on cooling deposits snow-white needles of frans-dichlorobis (thiourea)platinum (II). 

Cl5H23CIM0N2O6P2 f (Dicyanovinylidene)(ir-cyclopentadienyl)-trans-bis(trimethyl phosphite)chloromolybdenum(II), 40B, 753 C15H2flClN02Pt, Allyl ether platinum(II) chloride (a-methylbenzyl)amine complex, 38B, 738... 

CaH1gCl3Ns02Pt 3 H2O, trans-Nitrochloroamminediethylenetriamine-platinum(IV) chloride trihydrate, 45B, 1014 Ci,Hi 6Cli,Ni,03Re2 r Oxorhenium(V) ethylenediamine complex, 38B, 812 CftHigCluNftPt, cis-Dichlorobis(ethylenediamine)platinum(IV) chloride, 35B, 587... 

CbH2 2CI2Ne02Pt, trans Diamminebis(N-methy1 imidazole)platinum(11) chloride dihydrate, 38B, 906... 

Johnson and Whitehead have further shown that the reductive elimination of the pyrrolidine group from the pyrrolidine enamine of 2,4-dimethyl-cyclohexanone (16), which involved treating it with a mixture of lithium aluminum hydride and aluminum chloride (9), gave the trans isomer of 3,5-dimethyl-/l -cyclohexene (17) which on subsequent hydrogenation on a platinum catalyst led to the // onr-3,5-dimethylcyclohexane (18). 

Benkeser and Tincher 128>, on the other hand, reduced acetylenes preferentially to trans olefins using solvated electrons generated at a platinum cathode by electrolytic reduction of lithium chloride in methylamine [lithium metal is formed from lithium ion at the cathode in this electrolysis its dissolution in methylamine generates the solvated electron and regenerates lithium... 

Denmark pursued intramolecular alkyne hydrosilylation in the context of generating stereodefined vinylsilanes for cross-coupling chemistry (Scheme 21). Cyclic siloxanes from platinum-catalyzed hydrosilylation were used in a coupling reaction, affording good yields with a variety of aryl iodides.84 The three steps are mutually compatible and can be carried out as a one-pot hydro-arylation of propargylic alcohols. The isomeric trans-exo-dig addition was also achieved. Despite the fact that many catalysts for terminal alkyne hydrosilylation react poorly with internal alkynes, the group found that ruthenium(n) chloride arene complexes—which provide complete selectivity for trans-... 

Class b nucleophiles, notably the perfluorothiophenolate anion, attack the platinum, displacing one chloride (presumably that trans to the olefinic group). Methylmagnesium iodide acts as a source of I in this system rather than a carbanion-like species, and methyllithium causes total decomposition. 

It appears that one of these rate constants (kc or kt) is 10 times as large as the other and anyone who has worked in platinum chemistry will say, of course, that chloride has a greater trans effect than ammonia. These are both weak trans directors, but one would expect the fast reaction site to be the cw-chlorides in other words, the chloride which is trans to a chloride, the cis-diaquo isomer, is the one which should be formed rapidly. 

Cl2N202PtC6Hi4, Platinum(ll), c -dichlorobis-(propanoneoxime)-, 34 82 Cl2N202PtC6Hi4, Platinum(ll), trans-dichlom-bis(propanoneoxime)-, 34 83 Cl2N3PtC4Hi3, Platinum(ll), chloro(diethylene-triamine)-, chloride, 34 78 Cl2N3PtC9H23, Platinum(ll),... 

Gis-dichloro-diammino-platinum, [Pt(NH3)2Cl2], was first prepared by Peyronne.2 It is easily formed by adding ammonia to a cold solution of platinous chloride in hydrochloric acid, when a greenish-yellow voluminous precipitate separates. This is boiled with water and filtered hot, when, on cooling the filtrate, the substance crystallises in yellow microscopic needles. It is sparingly soluble in water, and is more pure yellow than the isomeric trans-compound. Both cis- and fraws-dichloro-diammino-platinum are obtained on heating tetrammino-platinous chloride with hydrochloric acid. 

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