Bridging Iodine Research Articles

The chemistry of polynuclear compounds. Part 30. Some reactions of dodecacarbonyltetrahydridotetraosmium: the molecular and crystal structure of trihydrido-µ2-iodo-cyclo-tetrakis(tricarbonylosmium)-(4Os–Os)

Dodecacarbonyltriosmium reacts with H2 under pressure to produce [Os4(CO)12H4] almost quantitatively. Methanolic K[OH] converts this into [Os4(CO)12H3]– which gives the title compound [Os4(CO)12H3l] with l2. Crystals of [Os4(CO)12H3l] are monoclinic, with a= 17.307(8), b= 8.040(3), c= 17.760(9)A, β= 119.80(2)°, space group C2/c, and Z= 4. The final residuals for 2 724 unique observed reflections are R 0.036 and R′ 0.039. The four Os atoms are in a ‘butterfly’ configuration: one edge has been extended and a bridging iodine inserted [Os-l 2.749(4)A]. A crystallographic two-fold axis passes through the iodine atom and bisects the opposite Os–Os bond. The Os–Os distances are 2.876(1)(two), 2.927(3), and 3.052(1)A(two): the crystallographic symmetry, 1H n.m.r. spectrum, and geometrical arrangements of the carbonyls indicate that the three longest Os–Os bonds are hydride-bridged. Methanolic Na(OMe) converts [Os4(CO)12H4] into [Os4(CO)11(CO2Me)H4]–, isolated as the [N(PPh3)2]+ salt.

Crystal structure of triiodobismuth(III)-tri-μ-iodo-tris(triphenylarsinoxide)-bismuth(III), C54H45As3Bi2I6O3

The crystals of the title compound are triclinic, with unit-cell dimensionsa =14.804(7),b =18.657(9),c = 22.955(13) A, α = 90.2(1), β 106.6(1), γ = 91.0(1) °, space groupP¯1, andZ = 4. The crystal structure has been determined from x-ray diffractometer data by direct methods and Fourier techniques, and refined by least-squares methods using 11,383 independent reflections (I> 2σ(I)) to anR value of 0.076. The structure consists of complex molecules with two distorted octahedra sharing a face. The first of the bismuth atoms is coordinated by six iodine atoms, three of them bridging, and the second by three bridging iodine atoms and three oxygen atoms of the triphenylarsinoxides. The orientation of the phenyl rings is the only significant difference between the two complex molecules in the asymmetric unit.

ChemInform Abstract: NUCLEAR QUADRUPOLE RESONANCE OF TELLURIUM TETRAIODIDE

Chemischer InformationsdienstVolume 7, Issue 11 Physical Inorganic Chemistry ChemInform Abstract: NUCLEAR QUADRUPOLE RESONANCE OF TELLURIUM TETRAIODIDE TSUTOMU OKUDA, TSUTOMU OKUDASearch for more papers by this authorKOJI YAMADA, KOJI YAMADASearch for more papers by this authorYOSHIHIRO FURUKAWA, YOSHIHIRO FURUKAWASearch for more papers by this authorHISAO NEGITA, HISAO NEGITASearch for more papers by this author TSUTOMU OKUDA, TSUTOMU OKUDASearch for more papers by this authorKOJI YAMADA, KOJI YAMADASearch for more papers by this authorYOSHIHIRO FURUKAWA, YOSHIHIRO FURUKAWASearch for more papers by this authorHISAO NEGITA, HISAO NEGITASearch for more papers by this author First published: March 16, 1976 https://doi.org/10.1002/chin.197611012AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume7, Issue11March 16, 1976 RelatedInformation

Nuclear Quadrupole Resonance of Tellurium Tetraiodide

Abstract The nuclear quadrupole resonance (NQ R) of 127I in tellurium tetraiodide was observed, and the Zeeman effect on a single crystal was examined. Tellurium tetraiodide shows ten resonance lines in the frequency range from 195 to 260 MHz. From the analysis of the zero-splitting patterns, it has become apparent that tellurium tetraiodide crystals contain eight nonequivalent iodine atoms, two of which yield large asymmetry parameters (94.9% and 73.8%) and small quadrupole coupling constants (775.07 MHz and 929.55 MHz) at room temperature. These two may be assigned to the bridging iodine atoms, but they differ markedly from each other in the temperature dependences of e2Q q/h and η. The other six iodine atoms have small η values and coupling constants of about 1600 MHz; they are assigned to the terminal atoms. From these results, it may be concluded that each tellurium atom has three terminal and two bridging iodine atoms.

The preparation and structure of μ-iodobis( h5-cyclopentadienyldicarbonyliron) fluoroborate

The identity and structure of a compound which arises frequently in the generation of ( h 5-C 5H 5)Fe(CO) 2 + ion from ( h 5-C 5H 5)Fe(CO) 2I and AgBF 4 have been determined. The substance was shown to be {[ h 5-C 5H 5)Fe(CO) 2] 2I}BF 4 s a compound already known from the work of Fischer and Moser. It consists of a BF 4 − anion and a cation formed by two ( h 5-C 5H 5)Fe(CO) 2, groups having the expected shape and dimensions, united by a bridging iodine atom. The FeI bonds have an average lenght of 2.588 » and the FeIFe angle is 110.8(1)°. The FeFe distance of 4.26 » is consistent with the expectation that there should be no metalmetal bond. Presumably the large FeIFe angle results from a compromise between the tendency of I to maximize p character in its bonding orbitals and the necessity of niminizing non-bonded contact between the ( h 5-C 5H 5)Fe(CO) 2 groups. Crystallographic data are: space group, P2/ a; unit cell dimensions, a=15.605(2)», b=9.607(2)», c=12.373(2)», β=104.86(1)°, V=1792.9(6)» 3; d ealc=2.10 g/cm 3 for Z=4; d obs=2.08±0.02 g/cm 3. Refinement using 1595 independent reflections with F o 2>3σ( F o 2 was terminated at residuals of R 1=0.076 and R 2=0.114.

129I Mössbauer Effect in Several Charge-Transfer Complexes of Iodine

The Mössbauer effect of the 27.8-keV transition in 129I has been studied in the iodine complexes I2·phenazine, I2·acridine, and I2·hexamethylenetetramine. The Mössbauer spectrum of the I2·phenazine complex has shown only one chemical species of iodine, whereas those of the other complexes have shown the existence of two species of bridging and terminal iodine. From the Mössbauer parameters such as the isomer shift, quadrupole coupling constant, and asymmetry parameter, the electron distribution on the iodine atoms in the complexes was calculated. In the I2·phenazine complex, 0.09e− is transferred to the iodine atom from the phenazine molecule. In the I2·acridine and I2·hexamethylenetetramine complexes, the charges on the bridging iodine atoms are decreased and those on the terminal atoms are increased. In the later complex, a net charge of 0.08e− is transferred to the iodine molecule through the nitrogen atom from the hexamethylenetetramine molecule.

The chemistry of π-cyclopentadienyl nitrosyl molybdenum complexes. Compounds containing bridging iodine and sulphur ligands

The syntheses and chemistry of the related binuclear complexes, [(π-C5H5)Mo(NO)X2]2, [(π-C5H5)Mo(NO)X]2, and [(π-C5H5)Mo(NO)(I)(SCH2Ph)]2(X = I, SCH2Ph or SPh) are reported. Examination of the complexes by mass spectral and i.r. techniques has shown that although the structures of [(π-C5H5)Mo(NO)X2]2 and [(π-C5H5)Mo(NO)(I)(SCH2Ph)]2 appear to be similar and to contain, probably, two bridging groups X, and two terminal X and NO groups, [(π-C5H5)Mo(NO)X]2 may contain only bridging groups, X and NO, and a Mo–Mo bond. The mixed ligand species, [(π-C5H5)Mo(NO)(I)(SCH2Ph)]2, is shown spectrally to exist as isomers, one of which contains bridging SCH2Ph groups and terminal I atoms.

Crystal and molecular structure of di-µ-iodo-bis-[(o-dimethylaminophenyl)dimethylarsine-As,N]-dicopper(I)

Di-µ-iodo-bis-[(o-dimethylaminophenyl)dimethylarsine-As,N]-dicopper(I) crystallizes in the orthorhombic system, space group Pbca, with Z= 4 in a unit cell of dimensions a= 11·34(3), b= 13·69(1), and c= 17·60(1)A. Diffraction data were used and the structure solved by the heavy-atom method and refined by least-squares methods to R 8·5%. The molecules are dimeric; each of the copper atoms in the dimer is surrounded by four ligand atoms in an approximately tetrahedral arrangement and there are two iodine bridges between each pair of copper atoms. The packing of the molecule makes the Cu ⋯ Cu distance (2·727 A) unusually short. Some distortion in the molecule is discussed in terms of the steric requirements of the ligand.

Catena-[µ-(o-phthaloyl-C,C′,O)]-µ-iodo-iodonickel(IV): crystal and molecular structure

The crystal structure of the title compound, a linear polymeric nickel compound with alternate iodine and carboxyl bridges and incorporating the unique carbon-bonded (o-phthaloyl-C,C′,O)2– tridentate ligand(I) has been determined.

Magnetism, electronic spectra, and structure of transition metal alkoxides. VIII. Nickel halo methoxides

The results of magnetic and spectral measurements of Ni(OMe)Cl and its solvates are interpreted in terms of clusters of four nickel atoms interacting ferromagnetically through 90� methoxy bridges. It is proposed that these clusters associate through chlorine bridges to form an infinite lattice. Solvation by methanol breaks only chlorine bridges so that the magnetic clusters are preserved. Stepwise replacement of chlorine by methoxyl resulted in the isolation of the expected compounds of composition Ni3(OMe)4Cl2 and Ni3(OMe)5Cl. Here, the magnetic isolation of the clusters disturbed by antiferromagnetic intercluster exchange. Bromine and iodine bridges also promote antiferromagnetic exchange but in contrast to the methoxy bridges, they may be broken by solvation with methanol.