Ni5(C5H5)4S4, a Pentanuclear Metal Complex Containing a Square‐Planar Nickel(0) Atom

Vahrenkamp, H.; Dahl, Lawrence F.

doi:10.1002/anie.196901441

Cited by 17 publications

(6 citation statements)

References 8 publications

(5 reference statements)

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“…This diamagnetic cluster features two pairs of Cp 2 Ni 2 (μ-SR) 2like subunits attached to a central planar nickel center. 21 The CpNi---NiCp distances of 2.495(3) Å in the cluster match the 2.4442(8) Å Ni−Ni bond in [1 edt ] + . In view of the new results, the cluster could be described as (CpNi 2.5 ) 4 (μ 3 -S) 4 Ni II , with antiferromagnetic coupling between the two [Cp 2 Ni 2 S 2 ] − centers, mediated by the square-planar Ni(II) center.…”

Section: ■ Results and Discussionmentioning

confidence: 65%

“…In view of the new results, the cluster could be described as (CpNi 2.5 ) 4 (μ 3 -S) 4 Ni II , with antiferromagnetic coupling between the two [Cp 2 Ni 2 S 2 ] − centers, mediated by the square-planar Ni(II) center. This perspective avoids the previous description that invokes square-planar Ni(0) …”

Section: Discussionmentioning

confidence: 82%

“…These findings suggest a revised description of Cp 4 Ni 5 (μ 3 -S) 4 . This diamagnetic cluster features two pairs of Cp 2 Ni 2 (μ-SR) 2 -like subunits attached to a central planar nickel center . The CpNi- - -NiCp distances of 2.495(3) Å in the cluster match the 2.4442(8) Å Ni–Ni bond in [ 1 edt ] + .…”

Section: Discussionmentioning

confidence: 94%

“…This perspective avoids the previous description that invokes squareplanar Ni(0). 21 Metal−Metal Bonding between 18e Metal Centers. The new results suggest that Cp 2 Ni 2 (pdt) has a low-lying paramagnetic state.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂

et al. 2016

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The effects of simple thiolates vs chelating dithiolates on M−M bonding, redox potentials, and synthetic outcomes have been probed experimentally and computationally. Nickelocene (Cp 2 Ni) has long been known to react with simple thiols to give diamagnetic Cp 2 Ni 2 (SR) 2 with planar Ni 2 S 2 cores and long Ni---Ni distances. Ethane-and propanedithiol (edtH 2 and pdtH 2 , respectively) instead give di-, tri-, and pentanickel complexes, with nonplanar Ni 2 S 2 cores. The 36e Cp 2 Ni 2 (pdt) (1 pdt ) adopts a symmetrical butterfly Ni 2 S 2 structure. Variable-temperature NMR spectra indicate that 1 pdt possesses a thermally accessible triplet state (ΔG = 2.65(5) kcal/mol) in equilibrium with a diamagnetic ground state. DFT calculations indicate that the singlet−triplet gap is highly sensitive to the nonplanarity of the Ni 2 S 2 core. The calculations further reveal that only the high-spin form of 1 pdt features Ni−Ni bonding, which is unprecedented. Cp 2 Ni 3 (pdt) 2 (2 pdt ), which derives from 1 pdt , crystallized as cis and trans isomers, both with a central Ni(pdt) 2 2− unit that is S,Schelated to two CpNi + centers. Reaction of Cp 2 Ni with 1,2-ethanedithiol (H 2 edt) and 1,2-benzenedithiol (bdtH 2 ) exclusively gave the trinickel species 2 edt and 2 bdt , which are structurally analogous to cis-2 pdt . Solutions of 2 edt are unstable, depositing crystals of Cp 2 Ni 5 (edt) 4 (3 edt ). Cyclic voltammetric studies show that the Ni 2 species oxidize readily to give the mixed-valence cations [1 pdt ] + and [1 edt ] + . Crystallographic and EPR analyses indicate that these cations are delocalized mixed-valence Ni(II)− Ni(III) species. Oxidation of Cp 2 Ni 2 (SEt) 2 , which features a planar Ni 2 S 2 core, afforded a mixed-valence cation, showing the pyramidal Ni 2 S 2 core observed in [1 pdt ] 0/+ and [1 edt ] 0/+ . Although not obtained from the Cp 2 Ni/H 2 edt reaction, the neutral complex 1 edt was obtained by reduction of [1 edt ] + . Variable-temperature NMR measurements and DFT calculations indicate that the triplet is further stabilized in this highly pyramidalized species.

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Section: ■ Results and Discussionmentioning

confidence: 65%

Section: Discussionmentioning

confidence: 82%

Section: Discussionmentioning

confidence: 94%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂

et al. 2016

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“…A major objective of these studies is to obtain a better understanding of the detailed nature of metal-metal interactions in transition metal cluster systems in that from the observed changes in molecular parameters due to the change in the number of valence electrons it has proven possible to deduce qualitatively the topological nature of the MO containing the least stable valence electrons. [1][2][3][4][5][6][7][8][9][10][11] The drastic influence of valence electrons on molecular geometry has been previously demonstrated from X-ray crystallographic measurements for metal cluster complexes in which the number of valence electrons has been varied by replacement with either different metal atoms and/or different ligands.1-9…”

Section: Sirmentioning

confidence: 99%

Molecular photochemistry. XXXVI. Photochemistry of some .alpha.-oxopropiophenones. Evidence for an unusual cyclic transition state for hydrogen abstraction

Turro¹,

Lee²

1970

J. Am. Chem. Soc.

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Nickel: Inorganic & Coordination Chemistry

Collinson

Schröder

2005

Encyclopedia of Inorganic Chemistry

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The general features and coordination chemistry of Ni 0 to Ni IV and complexation to cyanide, N‐, P‐, O‐, S‐, and halide‐donor ligands are detailed. The reactivity of Ni II complexes in the template synthesis of macrocycles and for the oligomerization and polymerization of alkenes are highlighted. The stabilization of radical Ni I and Ni III centers is related to the associated ligand types and metal‐ion stereochemistries. The supramolecular chemistry of Ni II includes the formation of aggregates, framework polymers, and receptors. The structures of a number of Ni‐containing enzymes have been elucidated and the formation of low‐molecular weight complex mimics is discussed.

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Ni₅(C₅H₅)₄S₄, a Pentanuclear Metal Complex Containing a Square‐Planar Nickel(0) Atom

Cited by 17 publications

References 8 publications

Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂

Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂

Molecular photochemistry. XXXVI. Photochemistry of some .alpha.-oxopropiophenones. Evidence for an unusual cyclic transition state for hydrogen abstraction

Nickel: Inorganic & Coordination Chemistry

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Ni5(C5H5)4S4, a Pentanuclear Metal Complex Containing a Square‐Planar Nickel(0) Atom

Cited by 17 publications

References 8 publications

Effect of Pyramidalization of the M2(SR)2 Center: The Case of (C5H5)2Ni2(SR)2

Effect of Pyramidalization of the M2(SR)2 Center: The Case of (C5H5)2Ni2(SR)2

Molecular photochemistry. XXXVI. Photochemistry of some .alpha.-oxopropiophenones. Evidence for an unusual cyclic transition state for hydrogen abstraction

Nickel: Inorganic & Coordination Chemistry

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Product

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Ni₅(C₅H₅)₄S₄, a Pentanuclear Metal Complex Containing a Square‐Planar Nickel(0) Atom

Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂

Effect of Pyramidalization of the M₂(SR)₂ Center: The Case of (C₅H₅)₂Ni₂(SR)₂