Platinum complexes, reactions with

Consequently, the presence of the SnCl2 promotes the reaction between molecular hydrogen and the platinum complex. Further, with PEt3 as tertiary phosphine, we have observed the P-31 spectrum of... 

A benzylic platinum complex treated with excess HCl results in the loss of MeCl, presumably via an unusual methylene transfer (Scheme 67). Ring opening by relief of strain is a useful route for C bond cleavage. The reaction of biphenylene with a series of Pt bisphosphine... 

The folded ring system (6 E = Me2NC) forms an r] S,S complex with platinum upon reaction with Pt(PPh3)4. ... 

One or two minor points may be added to Table 8 above the adducts of aldehydes and ketones to palladium and platinum complexes react with SO2, CO2 and NO2 with displacement of the organic moiety to give the products expected for addition of these molecules to a dioxygen complex diphenylacetylene displaces both the carbonyl and the dloxygen ligand Adducts of CS2 and thiourea have also been reported The products obtained with NO2 depend on the reaction conditions, especially the solvent reaction of NO2 with (r-BuNC)2M02 gives a trans dinitrate for M = Ni and a cis dinitrate for M = Pd ). 

A variety of metal acetylide-containing stars and dendrimers have been synthesized.329-332 Dendrimer 280 was prepared via reaction of a chloro-substituted platinum complex 278 with ethynyl functionalized dendron 279 in the presence of Cul (Scheme 2.73).329 This method generated dendrimers with up to 45 platinum units. 

In the case of propane it is necessary to take into account the possibility of the formation of the n- and i-propyl platinum complexes. An analysis of deuteropropane distribution makes it possible to determine the relative rates of platinum(II) reactions with primary and secondary carbon atoms. For this purpose the distribution of deuteropropanes in the case of platinum alkylation with n-PrHgBr and -prHgBr was investigated. The distribution of the deuteropropanes obtained by the H-D exchange of propane coincides with that detected for n-PrPt- and f-PrPt-derivatives if we accept that they are initially formed with a relative probability of 0.75 and 0.25, respectively. Taking into consideration that the propane molecule contains six primary and two secondary C-H bonds, it may be concluded that the selectivity... 

The stoichiometric reaction of platinum complex 184 with the cycloalkyne 185 also gives rise to cycloaddition products, 186 and 187 (Scheme 47), but these products were not formed in the reaction of 185 with l,2-bis(di-methylsilyl)benzene catalyzed by [Pt(CH2=CH2)(PPh3)2] <1997ICA(265)1>. 

Reductions of monosubstituted iron(iii) complexes have been studied, the reactions being inner sphere with rates in the order Br > Cl > F" in contrast to the corresponding europium(ii) systems. The order does, however, parallel that for the Cr reduction of pentammine-cobalt(m) halide complexes. Reactions with platinum(iv) complexes have been studied, and in the case of [Pt(NH3)sa] + and [Pt(NH3)sOH] + a two-electron change is involved with intermediate formation of Cr and subsequent production of dimeric Cr" complexes ... 

Examples of electrophilic addition of secondary phosphines to alkenes or alkynes were described. [114, 124, 125, 135]. Glueck [124-126] reported enantioselective tandem reaction of alkylated/arylation of primary phosphines catalyzed by platinum complex, proceeding with formation of chiral phosphaace-naphthenes. Palladium-catalyzed hydrophosphination of alkynes 219 tmder kinetic resolution conditions gave access to 1,1-disubstituted vinylphosphine boranes 220. However, despite screening several chiral ligands, temperatures, and solvents, the... 

Polymeric materials containing Pt—Pt bonds in their backbones have been examined (46). The formation of platinum polymers (23) was achieved via reaction of the platinum complex (21) with diacetylides, diphosphines, or diisocyanides (22) (eq. 7). 

Oxidative addition reactions to form metal alkyls or aryls have been observed for low-valent rhodium (37, 38), iridium 37, 39, 40), ruthenium 41), nickel 42), and platinum 11, 43, 44) complexes. Reactions with perfluoroalkyl halides extend this list to cobalt 45) and iron 46). Some examples are... 

If olefin platinum complexes react with olefins or acetylenes, the coupling reactions proceed [111-113]. In the reaction shown in eq. (21.39), the reaction mechanism is thought to be that first the vinyl compound of olefin is produced, followed by... 

A number of metal acetylide-containing dendrimers and stars have also been prepared." Scheme 25 shows the synthesis of a first-generation platinum acetylide dendrimer (87) containing 9 platimun complexes in its structure. Dendrimer 87 was made by the reaction of a chloro-substituted platinum complex (85) with an ethynyl functionalized dendron (86) in the presence of Cul." Dendrimers with up to 45 platinum emits were synthesized using this methodology. 

Cyclometallation reactions of trans-[Ml2(NH2CH2Ph)2l (M = Pd, Pt) occur quite differently.37 The platinum complex reacts with two equivalents of AgBP4 in acetone to produce Agl. Concentration of the filtered solution followed by dissolution in H20/Me0H and addition of KI generates the cyclometallated product. Scheme 6.8 ... 

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