Reshaping molecules through cocrystallization. Comparison of the structures of Hg{Co(CO)4}2 and Hg{Co(CO)4}2·C60·toluene

Bowles, Faye L.; Olmstead, Marilyn M.; Beavers, Christine M.; Balch, Alan L.

doi:10.1039/c3cc41773e

Cited by 6 publications

(7 citation statements)

References 25 publications

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“…An exception is represented by [Cu(dmpe) 2 ](2) [40], whose unit cell contains two independent anions, both containing two TBP-Co(CO) 4 groups, but one anion adopts a staggered conformation and the other an eclipsed conformation (Figure 4). A similar phenomenon has been observed for Hg{Co(CO) 4 } 2 , in which the two TBP-Co(CO) 4 groups may adopt a staggered or eclipsed conformation, and both have been characterized by SC-XRD [44].…”

Section: Resultssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 99%

“…TBP-Co(CO)4 groups may adopt a staggered or eclipsed conformation, and both have been characterized by SC-XRD [44]. TBP-Co(CO)4 groups may adopt a staggered or eclipsed conformation, and both have been characterized by SC-XRD [44]. A further isomer of 2 was reported as [PPN](2) salt [41], where a Co center is TBP and the second one displays a tetrahedral coordination of the four CO ligands, with Cu capping one edge of the Co(CO) 4 tetrahedron (Figure 4).…”

Section: Resultsmentioning

confidence: 99%

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Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

et al. 2021

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The reaction of [Co(CO)4]− (1) with M(I) compounds (M = Cu, Ag, Au) was reinvestigated unraveling an unprecedented case of polymerization isomerism. Thus, as previously reported, the trinuclear clusters [M{Co(CO)4}2]− (M = Cu, 2; Ag, 3; Au, 4) were obtained by reacting 1 with M(I) in a 2:1 molar ratio. Their molecular structures were corroborated by single-crystal X-ray diffraction (SC-XRD) on isomorphous [NEt4][M{Co(CO)4}2] salts. [NEt4](3)represented the first structural characterization of 3. More interestingly, changing the crystallization conditions of solutions of 3, the hexanuclear cluster [Ag2{Co(CO)4}4]2− (5) was obtained in the solid state instead of 3. Its molecular structure was determined by SC-XRD as Na2(5)·C4H6O2, [PPN]2(5)·C5H12 (PPN = N(PPh3)2]+), [NBu4]2(5) and [NMe4]2(5) salts. 5 may be viewed as a dimer of 3 and, thus, it represents a rare case of polymerization isomerism (that is, two compounds having the same elemental composition but different molecular weights) in cluster chemistry. The phenomenon was further studied in solution by IR and ESI-MS measurements and theoretically investigated by computational methods. Both experimental evidence and density functional theory (DFT) calculations clearly pointed out that the dimerization process occurs in the solid state only in the case of Ag, whereas Cu and Au related species exist only as monomers.

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Section: Resultssupporting

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

et al. 2021

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“…21) [269]. Similarly, co-crystallization of Hg[Co(CO) 4 ] 2 with C 60 in toluene produces a crystal were the cobalt complex rearranges to fit in the well-ordered fullerenes [270].…”

Section: Supportmentioning

confidence: 95%

“…The organometallic building blocks were [M(TPP(Ph) 4 The molecular packing indicate one-dimensional array induced by weak porphyrin-C 60 contacts, and these chains are held by weak C H· · · and van der Waals interactions (Fig. 20 [270], and cobalt corrole [271]. The reduction of a [Co(dppe)]Br 2 (dppe = bis(diphenylposphinio)ethane) and C 60 mixture in odichlorobenzene followed by precipitation of crystals by hexane allow to obtain an ionic complex of fullerene.…”

Section: Supportmentioning

confidence: 99%

Coordination chemistry on carbon surfaces

Axet¹,

Dechy‐Cabaret²,

Durand³

et al. 2016

Coordination Chemistry Reviews

112

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Isomerism in Molecular Metal Carbonyl Clusters

Cesari,

Femoni,

Forti

et al. 2024

Eur J Inorg Chem

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The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand‐protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M‐M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.

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Reshaping molecules through cocrystallization. Comparison of the structures of Hg{Co(CO)4}2 and Hg{Co(CO)4}2·C60·toluene

Abstract: Cocrystallization of Hg{Co(CO)4}2 with C60 produces Hg{Co(CO)4}2·C60·toluene in which the geometry of the Hg{Co(CO)4}2 molecule is rearranged to fit between the remarkably well ordered fullerenes.

Cited by 6 publications

References 25 publications

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

Polymerization Isomerism in Co-M (M = Cu, Ag, Au) Carbonyl Clusters: Synthesis, Structures and Computational Investigation

Coordination chemistry on carbon surfaces

Isomerism in Molecular Metal Carbonyl Clusters

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