Single-crystal neutron diffraction has allowed accurate characterisation of N-H...Pt and N-H...Cl interactions linking the two square-planar platinum(II) units which comprise the dianion of [NPr(n)4]2[PtCl4].cis-[PtCl2(NH2Me)2] 1: Pt...H 2.262(11) angstrom, N-H...Pt 167.1(9)-degrees; Cl...H 2.318(12) angstrom, N-H...Cl 151.0(12)-degrees. An extensive network of C-H...Cl hydrogen bonding between the cation and anion species is also revealed, and provides valuable information on what is one of the least well characterised types of hydrogen bond. A weak C-H...Pt interaction between one cation unit and the anion is also observed. In the light of this and particularly the stronger intra-anion N-H...Pt interaction, a new type of three-centre four-electron hydrogen bridge, involving a transition-metal atom, is proposed. Further supporting evidence is drawn from a re-evaluation of spectroscopic data for similar interactions previously reported. This type of interaction is contrasted with the more well known three-centre two-electron M-H half-arrow-pointing-right M, C-H half-arrow-pointing-right M, Si-H half-arrow-pointing-right M and B-H half-arrow-pointing-right M interactions and compared with conventional four-electron hydrogen bonds. Compound 1 is triclinic, space group P1BAR (no.2), Z = 2, with a = 10.680(4), b = 11.926(2), c = 15.350(15) angstrom, alpha = 93.88(4), beta = 100.57(5) and gamma 96.58(4)-degrees at 20 K. Final R(F2) = 0.124, S = 1.136 for 5244 F2 values (F0(2) > 0.0).

Structures of the complexes formed in aqueous solutions between zinc(II) and iodide ions have been determined from large-angle X-ray scattering, Raman and far-IR measurements. The coordination in the hydrated Zn2+ hexaaqua ion and the first iodide complex, [ZnI]+, is octahedral, but is changed into tetrahedral in the higher complexes, [ZnI2(H2O)2], [ZnI3(H2O)]− and [ZnI4]2−. The Zn-I bond length is 2.635(4)Å in the [ZnI4]2− ion and slightly shorter, 2.592(6)Å, in the two lower tetrahedral complexes. In the octahedral [ZnI(H2O)5]+ complex the Zn-I bond length is 2.90(1)Å. The Zn-O bonding distances in the complexes are approximately the same as that in the hydrated Zn2+ ion, 2.10(1)Å.

Neutron diffraction shows that the title compound contains both N–H ⋯ Cl and N–H ⋯ Pt bonds in the solid; such hydrogen bonding is considered to be responsible for the high solubility in dichloromethane of this and related adducts involving cis-[PtX2L2](X = Cl or Br, L = NH2Me or NHMe2) complexes which are otherwise practically insoluble.

Raman and infrared spectra of the stretching vibrational frequencies of mercury(II) halides in solvents with widely different solvating abilities, have been recorded and combined with literature data. The frequencies decrease as the interaction of the solvent with the mercury atom in the HgX2 entity increases. Using published data from structure determinations by X-ray diffraction in solutions and crystals, an empirical correlation of the XHgX angle and the frequency shift is obtained.

Neutron diffraction shows that the title compound contains both N–H ⋯ Cl and N–H ⋯ Pt bonds in the solid; such hydrogen bonding is considered to be responsible for the high solubility in dichloromethane of this and related adducts involving cis-[PtX2L2](X = Cl or Br, L = NH2Me or NHMe2) complexes which are otherwise practically insoluble.

ChemInformVolume 19, Issue 4 Organoelement Compounds ChemInform Abstract: Structure and Solvation of Mercury(II) Iodide and Bromide in Tetrahydrothiophene Solution. M. + SANDSTROEM, M. + SANDSTROEM Dep. Inorg. Chem., R. Inst. Technol., S-100 44 Stockholm, Swed.Search for more papers by this authorI. PERSSON, I. PERSSON Dep. Inorg. Chem., R. Inst. Technol., S-100 44 Stockholm, Swed.Search for more papers by this authorP. L. GOGGIN, P. L. GOGGIN Dep. Inorg. Chem., R. Inst. Technol., S-100 44 Stockholm, Swed.Search for more papers by this author M. + SANDSTROEM, M. + SANDSTROEM Dep. Inorg. Chem., R. Inst. Technol., S-100 44 Stockholm, Swed.Search for more papers by this authorI. PERSSON, I. PERSSON Dep. Inorg. Chem., R. Inst. Technol., S-100 44 Stockholm, Swed.Search for more papers by this authorP. L. GOGGIN, P. L. GOGGIN Dep. Inorg. Chem., R. Inst. Technol., S-100 44 Stockholm, Swed.Search for more papers by this author First published: January 26, 1988 https://doi.org/10.1002/chin.198804289Read the full textAboutPDF 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. Volume19, Issue4January 26, 1988 RelatedInformation

The structure of the solvated neutral Hgl2 and HgBr2 molecular complexes in tetrahydrothiophene (tht) solution has been studied by X-ray diffraction and vibrational spectroscopic methods. Pseudo-tetrahedral[Hgl2(tht)2]and [HgBr2(tht)2] species of approximately C2V symmetry are formed in solution. The Hg–I bond length is 2.670(4)A and the Hg–Br 2.535(6)A. The IHgl angle was found to be 143(2)° at 25 °C and BrHgBr 132(2)° at 30 °C including estimated corrections for shrinkage effects. Raman and i.r. spectra of the solutions and the solids are consistent with molecular models derived from the diffraction data. A comparison with crystal structure data for [HgBr2(tht)2] and [HgCl2(tht)2] is made.

Chemischer InformationsdienstVolume 16, Issue 48 Physical Organic Chemistry ChemInform Abstract: STRUCTURE AND SOLVATION OF MERCURY(II) IODIDE, BROMIDE, AND CHLORIDE IN PYRIDINE SOLUTION: REFINEMENT OF THE CRYSTAL STRUCTURE OF DIIODOBIS(PYRIDINE)MERCURY(II), (HGI2(PY)2) I. PERSSON, I. PERSSONSearch for more papers by this authorM. + SANDSTROEM, M. + SANDSTROEMSearch for more papers by this authorP. L. GOGGIN, P. L. GOGGINSearch for more papers by this authorA. MOSSET, A. MOSSETSearch for more papers by this author I. PERSSON, I. PERSSONSearch for more papers by this authorM. + SANDSTROEM, M. + SANDSTROEMSearch for more papers by this authorP. L. GOGGIN, P. L. GOGGINSearch for more papers by this authorA. MOSSET, A. MOSSETSearch for more papers by this author First published: December 3, 1985 https://doi.org/10.1002/chin.198548060Read the full textAboutPDF 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 onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References I. PERSSON, M. + SANDSTROEM, P. L. GOGGIN, A. MOSSET, STRUCTURE AND SOLVATION OF MERCURY(II) IODIDE, BROMIDE, AND CHLORIDE IN PYRIDINE SOLUTION: REFINEMENT OF THE CRYSTAL STRUCTURE OF DIIODOBIS(PYRIDINE)MERCURY(II), (HGI2(PY)2), J. Chem. Soc., Dalton Trans., 1985, 1597. DOI: 10.1039/dt9850001597; 10.1039/DT9850001597 Web of Science®Google Scholar Volume16, Issue48December 3, 1985 ReferencesRelatedInformation

The mechanism of platinum deposition onto carbon from a bath containing H2PtCl6 in 0.1 M HCl is discussed. Although voltammograms show multiple cathodic waves, it is shown that they all result from the reduction of Pt(IV) to Pt(0) and there is no evidence for Pt(II) as a stable intermediate at any potential; the multiple waves arise because the hexachloroplatinic acid exists in solution as a mixture of kinetically inert Cl−/H2O complexes. The nucleation of the Pt centres on carbon is a very slow process even with a large overpotential and this leads to surfaces with well dispersed hemispherical nuclei. Moreover, each Pt centre appears to grow only to a limiting size before growth ceases.

Etude par diffusion RX, spectres IR et Raman des modes de coordination autour des atomes Zn dans les differents complexes formes, Zn 2+ hydrate, ZnBr 4 2− , ZnBr 3 − et ZnBr 2 , ainsi que des longueurs de liaisons

Reactions of the anions [PtX3(CO)]–(X = Cl, Br, or I) with controlled amounts of formic acid and tri-n-propylamine in tetrahydrofuran lead to high yields of salts of [Pt2X4(CO)2]2– if appropriate cations are chosen. For Cl and Br derivatives with 13C-enriched CO (75%)195Pt and 13C n.m.r. studies are reported and values of 1J(PtPt) established. At 300 K there is exchange of CO between adjacent platinum atoms. Studies of 195Pt Fourier-transform n.m.r. spectra of the mixed halide species [Pt2XnY4–n(CO)2]2–(X,Y = Cl,Br; Cl,I; or Br,I) are interpreted on the basis of a marked preference for isomers with the higher atomic number halide on the Pt–Pt axis. For the Cl,Br system comparison between spectra obtained at 220 and at 300 K shows that at the higher temperature halide site exchange occurs on a given Pt atom, but is synchronised between both Pt atoms in the anion; this is interpreted in terms of the interplatinum atom exchange of the CO groups via CO bridging. Studies of the mixed halide species derived from [PtX3(CO)]– establish 195Pt shifts for fourteen of the eighteen possible species, and show that species with lower atomic number halide trans to CO are preferred.

AbstractDie Reaktionen der Anionen von (I) mit kontrollierten Mengen an Ameisensäure und Tripropylamin in THF liefern in hohen Ausb. die Anionen (II).

Reaffinement de la structure dans P2 1 /n (l'etude anterieure avait ete faite dans P2 1 ): affinement jusqu'a R=5,4%

Using F.t.i.r. and multiple acquisition methods, far i.r. spectra with fairly good S/N ratios can be obtained from aqueous solutions in about 4 hours. Spectra are presented for some concentrated ruthenium(III) chloride systems where the colour precludes Raman spectroscopy. To obtain spectra without interference from water or hydrated cations, quantitative subtraction techniques are employed for separate removal of each component. Results are presented for some indium(III) halide and gallium(III) bromide systems.

Vibrational assignments for Hg(C2H5)X (X  Cl, Br or I) and HgBr(C2D5) are proposed, on the basis of solution studies as far as possible. For the bromides, 21 force constants are refined in the presence of 12 constrained values from C2H5Cl and 12 of these are used as additional constraints in refining 9 force constants for the chloride and iodide. The nature of the normal modes of Hg(C2H5)C1 is discussed. The Hg-C stretching force constants of the ethyl compounds is marginally higher than in corresponding methyl derivatives.

Chemischer InformationsdienstVolume 9, Issue 50 Physical Organic Chemistry ChemInform Abstract: NUCLEAR MAGNETIC RESONANCE STUDIES OF SOME DIMETHYL SULFIDE AND DIMETHYL TELLURIDE COMPLEXES OF RHODIUM(III) S. J. ANDERSON, S. J. ANDERSONSearch for more papers by this authorJ. R. BARNES, J. R. BARNESSearch for more papers by this authorP. L. GOGGIN, P. L. GOGGINSearch for more papers by this authorR. J. GOODFELLOW, R. J. GOODFELLOWSearch for more papers by this author S. J. ANDERSON, S. J. ANDERSONSearch for more papers by this authorJ. R. BARNES, J. R. BARNESSearch for more papers by this authorP. L. GOGGIN, P. L. GOGGINSearch for more papers by this authorR. J. GOODFELLOW, R. J. GOODFELLOWSearch for more papers by this author First published: December 12, 1978 https://doi.org/10.1002/chin.197850061Read the full textAboutPDF 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 onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume9, Issue50December 12, 1978 RelatedInformation

AbstractDie Titelverbindungen (III) wurden durch Reaktion der Komplexsalze (I) mit den Hg‐ Verbindungen (II) erhalten.