Platinum , cyano complexes

Analogous cyano complexes can be prepared. Treating the bis chelate complex [Pt(dppm)2]2+ with 2 equivalents of NaCN leads to stabilization of the r 1-dppm complex (151) which can be used to prepare heterobimetallic bridging complexes with added M (M= Ag+/I, HgCl2, Rh2Cl2(CO)4) (equation 433).1461 Similar complexes can be formed with dialkyl and diaryl substituents on platinum in place of cyanide.1462... 

There have been reports of syntheses of cyano complexes in fused potassium cyanide, though the characterization of the products has not always been satisfactory.1 The dry reaction between potassium cyanide and potassium hexaiodoplatinate(IV), however, certainly gives the impure hexacyano-platinate(IV) and substitution of cycloocta-1,5-diene bonded to platinum(II) may be achieved by the use of solid potassium cyanide in the presence of a crown ether catalyst.16... 

Two sorts of metal—cyano complexes have been studied. The first contains an atom of zinc, cadmium, mercury or copper as the central atom, and the nitrogen quadrupole coupling is only a little higher than it is in nitriles (4.0—4.2 MHz against 3.8—4.0 MHz). In the second sort, the central atom is either platinum or cobalt and the observed couplings are markedly lower (3.47—3.68 MHz). 

A large primary hydrogen-deuterium kinetic isotope effect has also been reported in the hydrobis(phosphine) platinum(II) complex catalysed hydration of cyano groups (equation 85). The catalyst, ra .y-[PtH(H20)(PMe3)2][0H], is generated by treating the... 

Works of Other Researchers. Before 1930 studies on coordination chemistry in Japan were almost exclusively concentrated in Yuji Shibata s laboratory, and only a few reports from other laboratories were published. For instance, Satoyasu limori (1885-1982), who later became the founder of radiochemistry in Japan, studied the replacement of CN- groups in the hexacyanoferrate(III) ion with water in 1915 (38) and photochemical reactions of cyano complexes of platinum and nickel and photochemical cells in 1918 (39). 

By way of example, we can focus on the cyano complexes. Palladium and platinum can form homoleptic complexes with two, four, or six cyanides, depending on the metal oxidation state zero, two, and four, respectively. Rhenium forms heptacyano complexes in its - -3 and -t-4 oxidation states but forms an octacyano complex in its -t-5 state. Molybdenum and tungsten also appear commonly in octacyano complexes for +4 and - -5 oxidation states, and heptacyano analogs for the - -2 and - -3 cases, with only one occurrence of [Mo(CN)6]" anions in two oxidation states (n = 3, 4). Similar situations can be found with phosphine or carbonyl complexes. For instance, the group... 

In the c/r-cyano(cyanoacetylido)bis(triphenylphosphine)platinum(n) complex (70) the Pt-C(acetylido) distance of 1.96(3) A does not differ significantly... 

The compound 70 has also been reported showing the ambident character (both C- and N-coordination) of the cyano-stabilized ylide as ligand. The authors have also transposed their work concerning the keto-bis-ylide and palladium, with the synthesis of the C-bonded complex 71 or the new cycloplatinated or-thometallated compound 72. The latter by various treatments allows one to obtain other ylidic cationic complexes of platinum such as 73. A C,C,C-terdentate coordination of the keto bis-ylide, already observed with the palladium is also obtained from the reaction of 73 with gold derivatives. 

The reaction of cyclic nitrone with phenyl isothiocyanate <2003MI253>, isocyanate <1974JOC568>, or cyano-esters <1995JP11417> has been reported. The beneficial effect of activation of the dipolarophile by coordination on a platinum complex and focused microwave irradiation has been described (Scheme 15) <2003JCD2540>. 

Doubly bridged cationic diplatinum(II) complexes [Pt(o-CH2C6H4CN-fip )(2=P os)](BF4)2 have been synthesized by halide replacement. The cyano group remains bonded to platinum both in the solid state and in solution.492... 

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