Four-Coordinate Group-14 Elements in the Formal Oxidation State of Zero – Syntheses, Structures, and Dynamics of [{(CO)5Cr}2Sn(L2)] and Related Species

Kircher, Peter; Hüttner, Gottfried; Heinze, Katja; Schiemenz, Berthold; Zsolnai, László; Büchner, M; Driess, Alexander

doi:10.1002/(sici)1099-0682(199806)1998:6<703::aid-ejic703>3.0.co;2-h

Cited by 40 publications

(29 citation statements)

References 34 publications

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“…The asymmetric chelation pattern is reflected by the rotation of the molecules, whose long axis is not perpendicular to the direction of the MO rows, but tilted by approximately 5° (this is evident in both the STM rendering and the DFT model; see the Supporting Information, Figure SI.4). The calculated equilibrium bond length is close to the values reported for 3D copper carbonyl and solution‐phase inorganic complexes …”

Section: Resultssupporting

confidence: 83%

Two‐Dimensional Ketone‐Driven Metal–Organic Coordination on Cu(111)

Pia

Riello

Lawrence

et al. 2016

Chemistry A European J

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Two‐dimensional metal–organic nanostructures based on the binding of ketone groups and metal atoms were fabricated by depositing pyrene‐4,5,9,10‐tetraone (PTO) molecules on a Cu(111) surface. The strongly electronegative ketone moieties bind to either copper adatoms from the substrate or codeposited iron atoms. In the former case, scanning tunnelling microscopy images reveal the development of an extended metal–organic supramolecular structure. Each copper adatom coordinates to two ketone ligands of two neighbouring PTO molecules, forming chains that are linked together into large islands through secondary van der Waals interactions. Deposition of iron atoms leads to a transformation of this assembly resulting from the substitution of the metal centres. Density functional theory calculations reveal that the driving force for the metal substitution is primarily determined by the strength of the ketone–metal bond, which is higher for Fe than for Cu. This second class of nanostructures displays a structural dependence on the rate of iron deposition.

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Section: Resultssupporting

confidence: 83%

Two‐Dimensional Ketone‐Driven Metal–Organic Coordination on Cu(111)

Pia

Riello

Lawrence

et al. 2016

Chemistry A European J

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“…The M-N and M-O bond lengths in this structure are about 2.0-2.5 Å, which are consistent with expected bond lengths in solution-phase inorganic complexes. 39,40 The structure and bonding geometries of the metals on the surface differ from solution phase systems, 41 where structures with coordination numbers greater than four are common, suggesting the importance of the substrate in guiding the assembly of species which would otherwise partake in a Note that adding ligand to pre-deposited metal (c) produces the same 1D polymer structure as adding metal to pre-deposited ligand (Figures 1(a)-1(c)), i.e., final structure is independent of deposition order. diversity of bonding geometries.…”

Section: B Metal-ligand Polymer Chain Structurementioning

confidence: 99%

Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

Skomski

Tempas

Bukowski

et al. 2015

The Journal of Chemical Physics

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Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

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“…When a ratio of 1:1 is used, the isolated yield of 4 (as its Ph 4 P salt) is approximately 10%, along with other products in the reaction mixture. [{(OC) 5 [22,23] These compounds were, in fact, the main products from which the clusters had to be separated by chromatography. In the case of 5, the use of ethanol as the solvent instead of THF greatly improved the yield.…”

Section: Preparation Of Sn 6 Clustersmentioning

confidence: 99%