Five-Coordinate Hydrogen: Neutron Diffraction Analysis of the Hydrido Cluster Complex [H
 2
 Rh
 13
 (CO)
 24
 ]
 3−

Bau, Robert; Drabnis, Mary H.; Garlaschelli, Luigi; Klooster, Wim T.; Xie, Zuowei; Koetzle, Thomas F.; Martinengo, Secondo

doi:10.1126/science.275.5303.1099

Cited by 75 publications

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“…The carbonyl hydride cluster Ir 4 H 8 (CO) 4 (PPh 3 ) 4 (1) has been formed in high yield and purity by heating a mixture of Ir 4 (CO) 12 and PPh 3 in toluene at 90°C under hydrogen at atmospheric pressure. The product has been characterised by microanalysis, spectroscopy (IR, 1 H and 31 P NMR) and Xray diffraction.…”

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confidence: 99%

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Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

et al. 2003

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The carbonyl hydride cluster Ir4H8(CO)4(PPh3)4 (1) has been formed in high yield and purity by heating a mixture of Ir4(CO)12 and PPh3 in toluene at 90 °C under hydrogen at atmospheric pressure. The product has been characterised by microanalysis, spectroscopy (IR, 1H and 31P NMR) and X‐ray diffraction. In the solid state one hydrogen, one CO and one triphenylphosphane ligand are terminally bonded to each iridium atom, whereas four hydride ligands are bridging. All the hydrogen atoms were directly located by X‐ray analysis at an average H−Ir distance of 1.55 Å (for the terminal H) and 1.75 Å (for the μ‐H). As shown by 1H and 31P NMR spectra, two isomeric forms (1A and 1B) of the cluster are present in CD2Cl2 solution at room temperature, and they do not interconvert in the explored temperature range. However, if a solid sample of the cluster is dissolved at 188 K, only 1A is detected by NMR spectroscopy. The structure of 1B could be proposed on the basis of the T1 relaxation times of the various hydrides: it results by localised exchange of H and CO around two vertices of the tetrahedral frame. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…[2] Beside the most common terminal, bridging, and face-capping modes, [3] they can also occupy an interestitial coordination mode site, with up to six Hmetal interactions. [4,5] The hydride ligands in many clusters are abstracted from the solvent in which the cluster is prepared.…”

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Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

et al. 2003

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“…3-cluster complex [37]. Simultaneous refinement against XPD and NPD data has been successfully applied to the determination of hydrogen atom positions in the organic molecules chlorothiazide and hydrochlorothiazide [38], the simple hydrated salt Cs2C2O4.H2O [39] and has recently been shown also to be effective for complicated inorganic materials.…”

Section: Neutron Crystallography Of Molecular Materialsmentioning

confidence: 99%

“…The second is resolved on steady state source instruments such as D20 [ Figure 2; 54] and WOMBAT [55] by using a high take-off angle configuration (utilising a Ge (115) These instruments have the clear potential to offer suitable flux -resolution combinations for the study of hydrogenous powders (see, for example, the PND study of Li4BH4(NH2)3 using GEM [40]). However, wavelength-and sample-dependent attenuation corrections can add complications in fitting diffraction intensities across the full range of neutron energies in these data [37], and this must be taken into account in tackling experiments on highly hydrogenous materials. …”

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Neutron powder diffraction – new opportunities in hydrogen location in molecular and materials structure

Wilson¹,

Henry²,

Schmidtmann³

et al. 2014

Crystallography Reviews

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The potential of neutron powder diffraction in the location of hydrogen atoms in molecular materials and inorganic-molecular complexes is reviewed. Advances in instrumentation and data collection techniques that have made this field accessible are reviewed, along with a wide range of applications carried out by our collaboration investigating functional materials, hydrogen-containing minerals and molecular compounds. Some of the limitations in this area, particularly for molecular systems, are also addressed. IntroductionHydrogen is a key element whose functionality in inorganic material systems stretches from geochemical materials (e.g. clay minerals, cements), through key inorganic compounds (e.g. catalysts, co-ordination complexes and hydroxides/hydrates) and materials (e.g. polymers, hydrogen storage media, proton conductors/fuel cell components) to supramolecular and framework systems (e.g aluminosilicates, solvates and clathrates). The role of hydrogen in the structures (and hence derived applications) of these materials is thus of the utmost importance but one that, until recently, experimental methods generally failed to address, or could only do so in selected cases at great expense and considerable effort.Determination of the position of hydrogen in a material, whether it be a naturally occurring hydrate/hydroxide, a cement, a hydride/hydrogen storage material, a solvate or an organometallic compound has traditionally been difficult, time-consuming, expensive and imprecise, even where possible. However, knowledge of the distribution of hydrogen is central to understanding behaviours such as polymorphism, hydrogen bonding and three-dimensional structure definition, proton diffusion 2 pathways and levels of uptake in hydrogen storage materials, physical properties ranging from ferroelectricity to the elastic properties of polymers, and reaction mechanisms. Therefore the implementation and application of methodology that allows routine hydrogen position definition from readily available material (i.e. small easily synthesised quantities and in polycrystalline/small single crystal (≤50µm) form)is both of widespread application and key importance.In the work described here, development of the application of powder neutron diffraction methods in an optimised fashion to such materials is shown to have the capability to reveal structural information in a range of hydrogen-containing materials. A range of recent studies will be summarized, to illustrate the potential of this new capability. The powerful complementary use of both X-ray and computational methods with neutron powder diffraction in these studies will also be highlighted. The aim in this Review is not to provide a detailed account of the different materials studied, but to highlight the power of the methods of approach we have been systematically developing to access more accurate and different chemistry. It draws on a range of examples from our own collaborative work, which has recently focused on this theme [1].In this review, we have deli...

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[Pt19(CO)21(NO)]3− und [Pt38(CO)44]2−: Biegung einer Nitrosylgruppe durch intramolekulare Elektronenübertragung als Zwischenschritt bei der Bildung eines kubisch dichtest gepackten Platincarbonylclusters aus einem Polydecker

et al. 1999

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In memoriam Paolo ChiniVielkernige Carbonylmetallcluster (high-nuclearity carbonyl clusters, HNCCs) werden oft als ausgezeichnte Modellsysteme angesehen, anhand derer man Vorgänge, wie die Chemisorption und die katalytische Aktivität, die für kleine Metallpartikel von Bedeutung sind, untersuchen kann. Diese Vorgänge sind in hohem Maû von der lokalen Struktur der aktiven Stellen (exponierte Flächen, Oberflächendefekte, Knicke, Stufen) abhänging. [1] Zwar wurden in HNCCs einige Arten von Metallpackungen angetroffen, doch ist über Skelettumwandlungen, Kristallkeimbildungsvorgänge und die Aktivierung durch Liganden immer noch wenig bekannt. [2, 3] Vor einigen Jahren berichteten wir über die Herstellung und die Aufklärung der Kristallstruktur von [Pt 19 (CO) 22 ] 4À 1, dessen Hauptachse idealisiert fünfzählige Symmetrie aufweist. [4] Damals wurde aus der Reaktion von 1 mit protischen Säuren auch [Pt 38 (CO) 44 ] 2À 2 isoliert, doch machte die schlechte Qualität der Kristalle von 2, welche im Laufe der Jahre erhalten wurden, alle Versuche zunichte, seine Struktur vollständig aufzuklären. Das einzige, was herausgefunden wurde, ist, daû es sich um einen kubisch dichtest gepackten Pt 38 -Clusterkern handelt. [5] Infolgedessen konnte die Zahl der Kationen und Carbonylliganden nur aus Elementaranalysen [5] und theoretischen Erwartungen abgeschätzt werden. [6]Die auûerordentliche Redoxneigung von 1 und 2, auf die elektrochemische und spektroelektrochemische Untersu-Kristallabmessungen 0.7 Â 0.5 Â 0.2 mm; 2.2`q`22.78; 11 120 gesammelte Reflexe, davon 5612 unabhängig (R int 0.071); Verfeinerung von 536 Parametern mit 288 Restraints, max. Restelektronendichte 3.856 e À3 , R 1 0.065 (für F b 2s(F)) und wR 2 0.184 (alle Daten). Eine Fehlordnung einer Cyclohexylgruppe (C31 ± C36) wurde an zwei Positionen mit den Besetzungen 0.6/0.4 unter Verwendung von ADP-und Distanz-Restraints anisotrop verfeinert. Die Restelektronendichte von 3.856 e À3 wurde als Sauerstoffatom verfeinert, aber die Ergebnisse zeigen, daû nur eine teilweise Besetzung möglich wäre. Um die Struktur von 6 zu bestätigen, wurde die Geometrie von 6', eine leicht vereinfachte Variante von 6 (die iPr 2 N-Gruppen und die CH 3 -Gruppen am Siliciumatom wurden durch Wasserstoffatome ersetzt), optimiert. [24] Die Werte für die prinzipiellen Strukturparameter stimmen in den wesentlichen Aspekten gut mit den durch die Kristallstrukturanalyse von 6 gefundenen überein.

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Five-Coordinate Hydrogen: Neutron Diffraction Analysis of the Hydrido Cluster Complex [H ₂ Rh ₁₃ (CO) ₂₄ ] ³⁻

Cited by 75 publications

References 29 publications

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

Neutron powder diffraction – new opportunities in hydrogen location in molecular and materials structure

[Pt19(CO)21(NO)]3− und [Pt38(CO)44]2−: Biegung einer Nitrosylgruppe durch intramolekulare Elektronenübertragung als Zwischenschritt bei der Bildung eines kubisch dichtest gepackten Platincarbonylclusters aus einem Polydecker

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Five-Coordinate Hydrogen: Neutron Diffraction Analysis of the Hydrido Cluster Complex [H 2 Rh 13 (CO) 24 ] 3−

Cited by 75 publications

References 29 publications

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir4H4(μ‐H)4(CO)4(PPh3)4

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir4H4(μ‐H)4(CO)4(PPh3)4

Neutron powder diffraction – new opportunities in hydrogen location in molecular and materials structure

[Pt19(CO)21(NO)]3− und [Pt38(CO)44]2−: Biegung einer Nitrosylgruppe durch intramolekulare Elektronenübertragung als Zwischenschritt bei der Bildung eines kubisch dichtest gepackten Platincarbonylclusters aus einem Polydecker

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Five-Coordinate Hydrogen: Neutron Diffraction Analysis of the Hydrido Cluster Complex [H ₂ Rh ₁₃ (CO) ₂₄ ] ³⁻

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄

Synthesis, Solid‐State Structure and Multinuclear NMR Studies of the New Polyhydrido Iridium Carbonyl Cluster Ir₄H₄(μ‐H)₄(CO)₄(PPh₃)₄