Platinum mixed-valence complexes

Another type of complex for which it is obvious thatQlarge structural changes occur on excitation (probably 0.2-0.3 A) along particular coordinates are the infinite-chain mixed-valence complexes of platinum and palladium (class II, or localized mixed-valence complexes) (11).. These Pti [/PtIV, PdIVPtIV or Pdi [/PdIV... 

Results on a large number of linear-chain complexes of platinum are summarised in Table 11. Harmonic wavenumbers and anharmonicity constants have been determined in all cases. The normal coordinate seems to be related to the halogen movements involved in the proposed hopping process for the conductivity of these linear-chain mixed-valence complexes (95). The chain halogen atoms would need to move, on average, 0.54,0.38 and 0.22 A for chlorides, bromides and iodides, respectively, in order to reach the point midway between the two platinum atoms, i.e. to the situation of a platinum (III) chain. These values only differ by a factor of about two from the root-mean-square amplitudes of vibration of Vi in the Vj = 16 states these are calculated (91) to be 0.22 A for X = Cl (wi = 319.5 cm-i) and 0.20 A for X = Br (cji = 179.6 cm ). These distance changes are related to the shift in the equilibrium... 

The platinum blues are mixed-valence complexes containing discrete Pt chains (Figure 22.23). They are formed by hydrolysis of CM-[PtCl2(NH3)2] or cis-[PtCl2(en)] in aqueous AgN03 (i.e. replacing Cl by H2O... 

Tin, nitratodiphenyltris(dimethy) sulfoxide)-structure, 1,77 Tin, nitratotris(triphenyltin)-structure, 1, 47 Tin,tetrakis(acetato)-stereochemistry, 1,94 Tin, tetrakis(diethyldithiocarbamato)-angular parameters, 1, 57 Tin, tetrakis(ethyldithiocarbamato)-angular parameters, 1, 57 Tin, tetranitrato-stereochemistry, 1, 94 Tin, tri-n-butylmethoxy-, 3, 208 Tin alkoxides physical properties, 2, 346 Tin bromide, 3, 194 Tin bromide hydrate, 3,195 Tin carboxylates, 3, 222 mixed valence, 3, 222 Tin chloride, 3, 194 hydroformylation platinum complexes, 6, 263 Tin chloride dihydrate, 3,195 Tin complexes, 3, 183-223 acetyl ace tone... 

The A-frame hydride [Pt2H2(/i-H)(/i-dppm)2] undergoes reductive elimination of H2 in the presence of tertiary phosphine ligands, L, to give the platinum(I) dimer, [Pt2HL(//-dppm)2]. Hill and Puddephatt have shown that this occurs via the intermediate [Pt2II2(/i-H)L(//-dppm)2] (14).99 Carbon monoxide reacts rapidly and reversibly with [PtH(/r-PP)2Pt(CO)]+, PP = R2P-CH2-PR2, R = Et or Ph, to give [PtH(/i-PP)2Pt(CO)2]+ and [PtH(CO)(/u-PP)2Pt(CO)2]+, the first reported mixed valence, platinum(0)-platinum(ll) complexes.100... 

The preparation of various platinum-silyl complexes, including a platinum(II), platinum(IV), and mixed-valence platinum(II)-(IV) species, has been described.59 The treatment of one equivalent of 1,2-disilylbenzene with [Pt(PEt3)3] in toluene solution at 0°C affords [Pt(C6H4Si2H4)-(PEt3)2] (25) as a white powder the use of excess 1,2-disilylbenzene in the reaction leads to the formation of various platinum(IV) derivatives. 

The localized-valence halogen-bridged platinum(II)/platinum(IV) complexes (175) are of interest because of their highly anisotropic electrical and optical properties. The complexes are characterized by broad and intense intervalence bands in their electronic spectra.542 Partial oxidation of [PtCl(dien)]Cl with iodine yields the mixed valence species [PtI(dien)][PtI3(dien)]I2,543 but when 4Me-dien is used, the mixed valence compound is only obtained if it is trapped quickly, before isomerization of the meridional platinum(IV) complex to a facial form.544 Although these species nominally have localized valences, the extent of delocalization increases as the bridging halide... 

The eight-coordinate vanadium complex V(S2CMe)4 contains both dodecahedral and square prismatic eight-coordinate molecules in the same crystal.322 Of particular interest is the chain-like, mixed valence platinum complex [Pt2(S2CMe)4( i-I)]A, which displays unusual electrical properties metallic conduction between 300 and 340 K and semiconducting properties below 300 K,323 whereas the analogous nickel complex, [Ni2(S2CMe)4(p-I)]x is a semiconductor.324... 

From the neutral 1 2 complexes introduced before, two kinds of materials were obtained by electrocrystallization fully oxidized salts where both TTF CH= CH—py moieties are oxidized, and mixed valence salts in which the two ligands are partially oxidized. All oxidized complexes were obtained by oxidation at constant current of a neutral 1 2 complex in an electrolyte containing the anions, and using electrocrystallization technique with platinum wires (0 = 1mm) electrodes. 

Rate and equilibrium constant data, including substituent and isotope effects, for the reaction of [Pt(bpy)2]2+ with hydroxide, are all consistent with, and interpreted in terms of, reversible addition of the hydroxide to the coordinated 2,2 -bipyridyl (397). Equilibrium constants for addition of hydroxide to a series of platinum(II)-diimine cations [Pt(diimine)2]2+, the diimines being 2,2 -bipyridyl, 2,2 -bipyrazine, 3,3 -bipyridazine, and 2,2 -bipyrimidine, suggest that hydroxide adds at the 6 position of the coordinated ligand (398). Support for this covalent hydration mechanism for hydroxide attack at coordinated diimines comes from crystal structure determinations of binuclear mixed valence copper(I)/copper(II) complexes of 2-hydroxylated 1,10-phenanthroline and 2,2 -bipyridyl (399). 

Partially oxidized and mixed-valence platinum amine complexes 427... 

The macrocyclic phthalocyanine ligand will form a complex Pt(phthalocyanine).1106 The crystal structure shows two polymorphs present because of molecular packing.1107 The platinum is in a square planar coordination geometry with a mean Pt—N distance of 1.98 A. The complex can be partially oxidized with iodine to give conducting mixed valence solids.1108 Eighteen fundamental and overtone combination bands are observed in the resonance Raman spectrum of platinum phthalocyanine, and from this data the symmetry of the excited singlets are found to be Dy.. Qlv or D2.1109... 

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