Synthesis of functional heterometallic complexes and clusters containing molybdenum and palladium or platinum, their self-assembly on gold surfaces and X-ray photoelectron spectroscopic studies

Croizat, Pierre; Müller, Frank; Mantz, Hubert; Englisch, A.; Welter, Richard; Hüfner, S.; Braunstein, Pierre

doi:10.1016/j.crci.2008.12.004

Cited by 6 publications

(2 citation statements)

References 69 publications

(38 reference statements)

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“…(iv) In view of the high interest for the selective formation of self-assembly of highly ordered and oriented metal-organic monolayers on surfaces or the integration of metal complexes into mesoporous materials, 12 the deposition of S-terminated heterometallic complexes and clusters of Mo and Pd or Pt was studied on gold surfaces by scanning tunnelling microscopy (STM), ellipsometry, and X-ray photoelectron spectroscopy (XPS). 13 (v) The tetrahedral mixedmetal {RuCo 3 } carbonyl clusters functionalised with the phosphane-thiol ligands were studied on a gold surface by STM, XPS and X-ray absorption spectroscopy. 14 (vi) The chemical, structural, and thermodynamic characterisation of the mononuclear Pt(II) cis-complexes and the heterotrinuclear {Co 2 Pt} clusters containing N-substituted bis(diphenylphosphanyl) amine ligands with the pendant thiobenzyl ester groups 15 as well as a trinuclear Ag(I) complex and a Ag(I) coordination polymer with a thioether function in their short-bite diphosphine ligands 16 were described.…”

Section: Introductionmentioning

confidence: 99%

Thioether-terminated nickel(ii) coordination clusters with {Ni₆} horseshoe- and {Ni₈} rollercoaster-shaped cores

Schmitz

Leusen

Ellern

et al. 2016

Inorg. Chem. Front.

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We report two polynuclear nickel(II) compounds whose supramolecular structures are controlled by small inorganic templating anions and π-conjugated Schiff-base ligands (L·SMe 3− and HL·SMe 2− ) with peripheral, structurally exposed methylthioether groups. The central component of the compound [Ni 6 (L·SMe) 3 (CO 3 )(MeOH) 6 (THF) 2 ]Cl·2MeOH (1, monoclinic space group P2/c) displays a horseshoeshaped {Ni 6 } core templated by µ 6 -CO 3 2− moiety due to the fixation of atmospheric carbon dioxide.According to thermogravimetric analysis, compound 1 retains the structural integrity of its carbonatebonded metal core [Ni 6 (L·SMe) 3 (CO 3 )] + up to ca. 390°C. In the crystal lattice, compound 1 features an one-dimensional hydrogen-bonded chain structure [{CO 3 ⊂ Ni 6 }⋯Cl⋯{CO 3 ⊂ Ni 6 }] ∞ . The structure of the compound [Ni 8 (HL·SMe) 2 (L·SMe) 2 (OH) 4 (MeCN) 4 (H 2 O) 4 ](NO 3 ) 2 ·11MeCN·2PhCN (2, triclinic space group P1) consists of a dicationic crown-like {Ni 8 } metallamacrocycle hosting two NO 3 − anions in the upper and lower cavities. The {Ni 6 } complex is characterised by antiferromagnetic exchange interactions, whereas{Ni 8 } reveals predominantly ferromagnetic exchange coupling between the spin-1 Ni(II) centres. The presence of terminal thioether anchoring groups at the periphery of complex 1, coupled with high thermal stability and solubility in several common organic solvents, renders this compound an interesting candidate for molecular surface-deposition from solution using electrospray ionisation mass spectrometry approach and, possibly, for supported-transition metal complex heterogeneous catalysis.

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Section: Introductionmentioning

confidence: 99%

Thioether-terminated nickel(ii) coordination clusters with {Ni₆} horseshoe- and {Ni₈} rollercoaster-shaped cores

Schmitz

Leusen

Ellern

et al. 2016

Inorg. Chem. Front.

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“…While a large number of chiral sulfur ligands have been examined for use in asymmetric catalysis, bidentate Cp-sulfur ligands remain unexplored. A survey of literature reports of bidentate Cp-sulfur metal complexes reveals that a range of sulfur-containing functional groups, such as thiophene, thiolate, dithiocarboxylate and thioamide, dithioacetal and trithioortho ester, and, most commonly, thioether, have been incorporated, but the majority of the complexes are achiral. There are only two previous examples of planar chiral bidentate Cp-sulfur metal complexes, both prepared in racemic form: the cobalt complex D and the ruthenium complex E (which was obtained as a 1:1 mixture of two of the four possible diastereomers resulting from the generated planar and metal-centered chiral elements, with the nature of the isomerism not unambiguously determined).…”

Section: Introductionmentioning

confidence: 99%

Stereospecific Syntheses and Structures of Planar Chiral Bidentate η⁵:κS-Indenyl-Sulfanyl and -Sulfinyl Complexes of Rhodium(III)

et al. 2012

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Axially chiral rac-1-(2-methyl-1H-inden-3-yl)-2-(methylsulfanyl)naphthalene (rac-3) was synthesized from methyl 2-(methylsulfanyl)-1-naphthoate through reaction with the di-Grignard reagent derived from 1-bromo-2-(2-bromopropyl)benzene, followed by acid-catalyzed dehydration of the intermediate indanol. Oxidation of rac-3 with m-CPBA gave the diastereomeric sulfoxides (aR*,R S *)-5 and (aR*,S S *)-6, with the relative configuration of 5 established using single-crystal X-ray diffraction. The dichloro[η 5 :κS-indenylsulfanyl and -sulfinyl]rhodium complexes rac-4, (pR*,S S *)-7, and (pR*,R S *)-8 were synthesized through reaction of the ligands rac-3, (aR*,R S *)-5, and (aR*,S S *)-6, respectively, with rhodium trichloride in 9:1 methanol/water solution heated under reflux. The use of water as a cosolvent was found to be critical for obtaining good yields in the complexation reactions. Solid-state structures for the racemic rhodium complexes were determined through single-crystal X-ray diffraction. The enantiomers of the ligands 3, 5, and 6 were obtained in high enantiopurity through subjecting rac-3 to a series of Kagan asymmetric sulfoxidation, deoxygenation, and resulfoxidation reactions. The enantiomeric relationship of the rhodium complexes derived from the enantio-enriched ligands was confirmed by CD spectroscopy, and the high enantiopurity of the complexes established by 1 H NMR analysis using the chiral shift reagent Eu(hfc) 3 . The absolute configurations of the nonracemic ligands and rhodium complexes were established by a singlecrystal X-ray diffraction determination of the solid-state structure of (pS,S S )-8, with the Flack parameter refining to 0.00(2). ■ INTRODUCTIONPlanar chiral ferrocenyl ligands have been successfully utilized in a wide range of asymmetric transition-metal-catalyzed reactions. While the iron center does not participate directly in the catalytic cycle of these reactions, the chemical robustness of ferrocenes has the advantage of enabling numerous synthetic transformations that allow for the introduction of a variety of different coordinating groups, together with specific strategies for the stereoselective creation of the planar chiral element. 1 Planar chiral transition-metal complexes where the metal involved in the planar chiral element is also the site for catalysis have also been examined as asymmetric catalysts. The most successful examples to date are early transition-metal and lanthanide metallocenes, in particular ansa-metallocenes, where a tether between the cyclopentadienyl (Cp; we also use this abbreviation to cover related indenyl and fluorenyl systems) rings prevents the normally facile rotation around the Cp−metal axis, creating a well-defined steric and electronic environment around the metal. 2 As an extension of this development, planar chiral constrainedgeometry half-sandwich metal complexes would appear to be an attractive target for use in asymmetric catalysis. Takahashi and Onitsuka and their co-workers have, for example, demonstrated that planar chiral ruthen...

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Molybdenum

Tsai

2021

Comprehensive Coordination Chemistry III

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Synthesis of functional heterometallic complexes and clusters containing molybdenum and palladium or platinum, their self-assembly on gold surfaces and X-ray photoelectron spectroscopic studies

Cited by 6 publications

References 69 publications

Thioether-terminated nickel(ii) coordination clusters with {Ni₆} horseshoe- and {Ni₈} rollercoaster-shaped cores

Thioether-terminated nickel(ii) coordination clusters with {Ni₆} horseshoe- and {Ni₈} rollercoaster-shaped cores

Stereospecific Syntheses and Structures of Planar Chiral Bidentate η⁵:κS-Indenyl-Sulfanyl and -Sulfinyl Complexes of Rhodium(III)

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Synthesis of functional heterometallic complexes and clusters containing molybdenum and palladium or platinum, their self-assembly on gold surfaces and X-ray photoelectron spectroscopic studies

Cited by 6 publications

References 69 publications

Thioether-terminated nickel(ii) coordination clusters with {Ni6} horseshoe- and {Ni8} rollercoaster-shaped cores

Thioether-terminated nickel(ii) coordination clusters with {Ni6} horseshoe- and {Ni8} rollercoaster-shaped cores

Stereospecific Syntheses and Structures of Planar Chiral Bidentate η5:κS-Indenyl-Sulfanyl and -Sulfinyl Complexes of Rhodium(III)

Molybdenum

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Thioether-terminated nickel(ii) coordination clusters with {Ni₆} horseshoe- and {Ni₈} rollercoaster-shaped cores

Thioether-terminated nickel(ii) coordination clusters with {Ni₆} horseshoe- and {Ni₈} rollercoaster-shaped cores

Stereospecific Syntheses and Structures of Planar Chiral Bidentate η⁵:κS-Indenyl-Sulfanyl and -Sulfinyl Complexes of Rhodium(III)