Of trans Pt

In the case of the trans-complex, only the two chloride ions are substituted, the trans-effect of ammonia being too low to give substitution with the result that white needle crystals of trans-[Pt(NH3)2(tu)2]Cl2 are formed [73],... 

Fig. 4.8 Plots of pseudo first-order rate constants at 30 °C vs [nucleophile, Y] for reaction of trans-Pt(py)2Cl2 in methanol.

The increase in reaction rate is accompanied by a decrease in activation energy. The reaction rates of trans [Pt(PEt3)2LCl] with pyridine show the approximate trans effect order (J). 

The preparation of the complex requires about 3 h. A solution of phen (0.180 g, 1 mmol, 99%) in 10 mL of dichloromethane is added dropwise to a stirred solution (10 mL) of trans-[Pt(Me2SO)2MeCl] (0.401 g, 1 mmol) in the same solvent. The reaction mixture rapidly turns orange and a solid of the same color precipitates. After 20 min the precipitation is completed by adding 20 mL of diethyl ether and cooling at — 30°C for 2 h. The precipitate is collected by filtration and washed with 5 mL portions of cold methanol and then with diethyl ether. The yield was 0.42 g (98% based on trans-[Pt(Me2SO)2MeCl]). 

The reaction of trans-Pt with two equivalents of GSH results in a monomeric complex in which two GS units are coordinated via the cys-S atom [Eq. (10)] (76,131,189). The unstable intermediate species, [trans-Pt(NH3)2(GS)Cl] and [frans- Pt(NH3)2Cl 2GS], could also be detected by Berners-Price (189). The reaction of [Pt(NH3)3Cl]Cl with two equivalents of GS- initially yields [Pt(NH3)3GS], which reacts further, eventually forming [irans-Pt(NH3)2(GS)2] and free NH3 [Eq. (11) (131). This is rationalized by the large trans effect of the coordinated sulfur and the presence of a second nucleophilic sulfur. Therefore, the amine ligand is easily substituted by a second GS" unit. 

Activation parameters lor the reaction of trans-[Pt(PgtJ)2[2,4,6.Me3C(SHJ)Br] with 1 and with SQNHjfo in methanol ... 

Suppose a series of complexes of trans- [Pt(NH3)2LCl] is prepared where L is NH3, Cl-, N02 , Br , or pyridine (C5H5N). If the position of the Pt-Cl stretching band is determined for each complex, arrange the values in the order of increasing wave number (cm-1) for the series of ligands L and explain your answer. 

This route is little used, and only for complexes containing bonds between silicon and platinum, ruthenium or molybdenum. Products are obtained in high purity and good yields. The first application was in the synthesis of trans-[Pt(SiR3)(X)(EMe2Ph)2] (X = Cl or Br E = P or As) ... 

A similar mechanism involving an initial oxidative addition of HX to form a hydroplatinum intermediate may occur in the reaction of trans-Pt(C=CPh)2(PPh3)2 and j-Pt(C=CPh)2(PPh3)2 with HCl to form PtCl(C=CPh)(PPh3)2 and PtCl2(PPh3)2, respectively 111) ... 

The complex (54) shows vCN of the isocyanide ligand at 2323 cm 1.283 IR and Raman spectra of trans- Pt CH), where X = Cl, Br or I, gave the vCN mode assignments shown in Table 8.284 DFT calculations gave vibrational... 

Figure 3.45 H NMR spectrum of trans-Pt(PEt1)2HCl in benzene solution. The r scale can be converted to the 6 scale now used by the relationship 6 = I0 - r. (Reproduced with permission from Proc. Chem. Soc.. 1962, 321.)...

A number of unimolecular photoredox reactions have been studied. Kirk and Porter [130] reported a AF value of +4.8 cm3 mol"1 for the charge-transfer photolysis of Co(NH-,)5Br24 and suggested the formation of a caged radical pair, Con(Br ), from the LMCT excited state. Dissociation of this radical pair to the reaction products was suggested to account for the increase in volume as reflected by the positive volume of activation. Charge-transfer photolysis of trans -Pt(CN)4(N3)2 results in the reductive elimination of azide to produce Pt(CN) and dinitrogen [131,132], On... 

NH3 H2O-acetone (30-70) trans-[PtH(NH2R)- (PPh3)2] (R = H or Me) potentiometric titration with acid Measured instability constants for removal of NH2R by solvent. The presence of hydride decreases strength of trans-Pt NH2R bond a... 

TABLE 17.8 Rate constants for the square planar substitution reaction of trans-[Pt(py)2CI CI] with Cl as a function of the coordinating ability of the solvent. 

Figure 4. Addition of the group moments of the thioether functions in two different conformers of trans- [ Pt X2(SR2)2].

---