H. J. Keller

Highly conducting phenazine-doped 5,10-dihydro-5,10-dimethylphenaziniumyl–TCNQ. Physical properties and crystal and molecular structure

5,10-Dihydro-5,10-dimethylphenaziniumyl 7,7,8,8tetracyano-p-quinodimethanide (M2P-TCNQ) can be doped chemically with neutral phenazine (P). We investigated single crystals of a phase with composition Po.4(M2P)o.6TCNQ, i.e. (C 12HaN2)o.4(C 14HI4N2)o_.6(C 12H4N4) , C25.2 n15.6N6, M r = 402.44, triclinic, P1, a = 3.843 (3), b = 7.730(6), c = 16.028 (11) A, a -91.93 (6), fl = 93.56 (6), y = 94.57 (5) ° , V = 4 7 3 A 3 , Z = 1, d c = 1.41 Mg m -3. The structure was solved by direct methods and refined by least squares to R = 0.073 for 704 independent diffractometer data. The structure consists of segregated regular stacks of TCNQ and of dimethyl0567-7408/80/061435-06501.00 phenazine doped with 40% phenazine. Interplanar distances are 3.26 (1) A, in the TCNQ and 3.44 (1) A in the M2P stacks. The structure, the EPR data between 100 and 380 K and the electrical conductivity at room temperature are all very similar to those of N M P TCNQ.

NEW LINEAR CHAIN MIXED‐VALENCE PLATINUM COMPLEXES WITH AND WITHOUT HALIDE BRIDGES*

The mixed-valence chemistry of platinum has been arousing the interest of chemists for more than a century, even though it took a long time before the mixed-valence character was recognized. As early as 1842, Knopl obtained copper-like crystals on oxidizing K,Pt(CN), with chlorine. In 1855 Schafarik2 observed the formation of lustrous substances when handling cyanoplatinates. The oxidation of K,Pt(CN), by H N 0 3 to copper-like needles was reported by Weselsky’ in 1856. Wilm4 reanalyzed the oxidation product of K2[Pt(CN),] with chlorine and found a composition, K2[Pt(CN)4]Clo.33 1 1H20. In 1896 Werner’dealt with oxidation reactions on compounds K[PtC13a] (a = N H 3 , pyridine) and K2[Pt(oxalate)2]. The possibility of oxidizing Peyrone’s Chloride, cis-PtClz(NH3)2 with air was reported in 1886, followed by a detailed study by Tschugajeff and coworker^^,^ on theoxidation reactions with 02, 03, S 2 0 ~ ~ , H202. The reaction of Peyrone’s Chloride with sulfuric acid yielding a black substance with incorporated sulfato groups was observed by Drew’ and reinvestigated by Gillard and Wilkinson.” From crystallographic data, the compoung was assumed to have a Pt-Pt chain with an intermetallic separation of 3.06 A. Cahenl’ repeated the oxidation of Peyrone’s Chloride by (NH4)2S208. The product is different from the one described by Gillard and Wilkinson and contains, from ESCA measurements, two kinds of platinum species. Different products form when the oxidation of Peyrone’s Chloride is carried out in the presence of K2[PtCI4]’ or (NH4)2PtC16.11 Coppery needles were obtained, the ESCA spectra of which show only one kind of platinum. It must be noted that all the oxidation reactions of C~S-P~CI , (NH,)~ cited above work with the cis form of the complex only. Oxidation reactions to (presumably) mixed-valence systems have been reported with other platinum compounds, too, e.g. [Pt(NH3)4]2+,’2 “MGS”[Pt(NH,),][PtC14]7*13 and PtenC12.7 According to our present knowledge, two types of structures can form on oxidizing platinum(I1) compounds if the oxidation does not run straight to Pt(1V). They are chains of directly interacting platinum atoms such as in the partially oxidized te t ra~yanoplat inates , ’~ or chains of alternating Pt(I1)Pt(1V) species linked by bridging halogens, the Wolffram’s Salt analogs.15 In the

Crystal and molecular structure of di-iodotetrakis(phenyl isocyanide)cobalt(II). A strictly linear Co–I–Co bridge

The spin exchange between the cobalt(II) ions in the diamagnetic modification of (PhNC)4CoI2 is achieved through a strictly linear Co–I–Co bridge; the compound crystallizes as µiodo-bis[iodotetrakis(phenylisocyanide)cobalt(II)] iodide, [I–Co(L)4–I–Co(L)4–I]+I–(L = PhNC).

Zur Darstellung von η5-Cyclopentadienyl(dicarbonyl)-[η2-diethylamino(methylthio)carben]wolfram durch Thiomethylierung von η5-Cyclopentadienyl(dicarbonyl)diethylaminocarbinwolfram

Abstract Dicarbonyl(η 5 -cyclopentadienyl)(diethylaminocarbyne)(tungsten reacts with dimethyl(methylthio)sulfonium tetrafluoroborate to form dicarbonyl(η 5 -cyclopentadienyl)[η 2 -diethylamino(methylthio)carbene]tungsten in high yields.

Synthesis and Reactions of η2 -Carbene Complexes

Dicarbonyl(cyclopentadienyl)carbyne complexes of tungsten display a distinct nucleophilic character of the tungsten carbyne carbon triple bond. Cp(CO)2W≡CNEt2 reacts with protic acids to give diethylaminocarbene complexes. The corresponding alkyl and aryl carbyne complexes react in a stepwise manner with SMe+ cations to yield first η2-thiocarbene complexes and then dithiatungstabicyclo[1.1.0]butane complexes. Comparable η2-phosphinocarbene complexes are obtained on mild thermolysis of tungstaphosphabicyclo[1.1.0]-butanone cations.

Structure of Dibromo(1,2-diaminoethane)palladium(IV)-bis(1,2-diaminoethane)- palladium(II) Tetrakisperchlorate, [Pd(en)2Br2][Pd(en)2](ClO4)4

Orthorhombic [Pd(C2H8N2)2Br2][Pd(C2H8N2)][ClO4]4, C8H32Br2Cl4N8O16Pd2, Mr = 890.42, crystallizes in space group Iba2, a = 9.651(2), b = 13.951(8), c = 10.771(2) Å, Z = 2, V = 1412.80 Å3, dc = 2.05 g cm-3, R = 0.0564 for 1545 unique reflections. Data collection: MoKα, λ = 0.71069 Å, room temperature. The structure is a typical Wolffram’s Salt Analogue (WSA) with infinite stacks of planar [Pd(en)2]2+,4+ complex cations bridged by bromides. The ligands are three-dimensionally ordered. Intra-chain and inter-chain hydrogen bridges link the ligands with the perchlorate counter ions which occupy statistically two different orientations. Diffuse sheets appear together with Bragg reflections for 1 odd layers indicating a thermally activated motion of the bromides in chain direction. This model was confirmed with temperature dependent Weissenberg work

Structure of the Linear-Chain Mixed Valence Compound Bis(l,3-diaminopropane)platinum(II)bis(l,3-diaminopropane)- diiodoplatinum(IV)tetraperchlorate

The title compound C12H49Cl4I2N8O 16Pt2, Mr 1314.1, is monoclinic P 21 (from structural analysis), a = 8.74(1), b = 11.36(1), c = 8.63(1), β = 107.6(5), V = 817 Å3, Z = 1, Dm (flotation) = 2.65 g cm-3, Dc = 2.66 g cm-3, MoKɑ λ = 0.71069, μ = 110.7 cm-1, R = 0.063 for 1068 observed reflections. Rotation photographs show diffuse patterns corresponding to odd values of k together with weak Bragg reflections. Refinement of diffractometer data was carried out in space groups Pm, P21/m and P21; both refinement in Pm and P21 give satisfactory agreement and lead to very similar crystal structures

Structure of a Pt(II)-Pt(IY) Mixed-Valence Linear Chain Complex: Bis (1,2-diaminopropane )platinum(II)bis (1,2-diaminepropane ) - dibromoplatinum(IV)tetraperchlorate

[Pt(C3H10N2)2][Pt(C3H10N2)2Br2](ClO4)4 crystallizes as flat orthorhombic needles with cell dimensions: a = 7.74(1); b = 11.14(2); c = 19.42(3) Å, Z = 1. Since rotation photographs showed diffuse patterns corresponding to odd values of k without any Bragg reflections, the subcell for which b = 5.57(1) Å was adopted for the structural analysis; it has systematic absences consistent with space groups Pc 2 a and Pcma; the structure was refined in both space groups by least squares and difference Fourier syntheses to R = 0.062 in Pc 2a and R = 0.064 in Pcma. A final decision between the two space groups proved to be impossible within the scope of the experiment. An analysis of the “diffuse” layers reveals that the bridging bromines vibrate in a one-dimensional collective mode within a lattice of “uniform”, fixed platinum cations.

Crystal and Molecular Structure of 4-Oxo-6-iodoqwnolinium(OIQn)-2,2'- (2,5-cyclohexadiene-1,4-diylidene)- bispropanedinitrile (TCNQ)

Abstract One-dimensional Conductors, Linear Chain Structures (C9H7INO · C12H4N4) triclinic PT, a = 7.161(5) Å, b = 8.639(5) Å, c = 17.392(6) Å, α -64.96(4)°, β = 80.64(3)°, γ = 76.99(3)°, V = 1075.6 Å3 , Z = 2, dc = 1.47 Mgm-3. The structure was refined to R - 0.114 for 2022 reflections. It consists of segregated diadic stacks of TCNQ and 4-oxo-iodoquinolinium ions. Inter-planar distances in the TCNQ stack are 3.09(1) Å and 3.32(1) Å; 3.37(1) Å and 3.55(1) Å in the quinolinium stack.

Kristall- und Molekülstruktur von Tetrakis(4-fluorophenylisonitril)rhodium(I)chloridhydrat und Tetrakis(4-nitrophenylisonitril)rhodium(I)chlorid / Crystal and Molecular Structure of Tetrakis(4-fiuorophenylisonitrile)rhodium(I) Chloride Hydrate and Tetrakis(4-nitrophenylisonitrile)rhodium(I) Chloride

Abstract 4-Fluorophenylisonitrile and 4-nitrophenylisonitrile react with μ-dichloro-bis[dicarbo-nylrhodium(I)] [Rh(CO2)Cl]2 yielding the blue tetrakis(4-fluorophenylisonitrile)rhodium-(I)chloride hydrate (1) and the dark green tetrakis(4-nitrophenylisonitrile)rhodium(I) chloride (2). Yellow Perchlorates 3 (of 1) and 4 (of 2) can be obtained from both compounds. 1 crystallizes in the monoclinic space group P 21/c with a - 10.57(2) Å, b = 11.459(5) Å, c = 23.71(5) Å, β = 107.14(4)°, Z = 4. Compound 2 crystallizes in the triclinic space group P1̄ with a = 12.34(4) Å, b = 10.704(3) Å, c = 13.703(3) Å, α = 106.58(2)°, β = 106.07(4)°, γ = 108.29(3)°, Z = 2. 3 belongs to the rhombic space group Pnmm or Pnm2 with a = 11.523(4) Å, b= 15.48(1) Å, c= 15.915(9) Å, Z = 4 and 4 is triclinic with a = 6.987(4) Å, b = 14.300(7) Å, c == 16.983(7)1, α = 71.89(3)°, β = 89.20(4)°, γ = 79.54(4)°, Z = 2. The structures of 1 and 2 were determined by Patterson and Fourier methods from diffractometer data and refined by least squares to R - 0.062 (1) or R = 0.157 (2). Crystals of both compounds contain metal-to-metal bonded dimers with a Rh-Rh bond distance of 3.207(2) Å in 1 and 3.25(1) Å in 2. the ligands of the two adjacent complex units taking an eclipsed position. These dimers are arranged in layers. There is a second type of layer in 1 containing the water molecules which are hydrogen bonded to the chloride counterions. The blue color of 1 is caused by a strong absorption at 16700 cm-1 (597 nm). 2 has a similar absorption band at 16500 cm-1 (606 nm). Compounds 3 and 4 contain the monomeric complex units.