Crystallographic evidence for copper-copper bonding at 2.8 Ang. Crystal and molecular structure of tetrakis(tetraphenylphosphonium) hexakis(1,2-dithiosquarato)octacuprate(I)

Hollander, Frederick J.; Coucouvanis, D.

doi:10.1021/ja00824a095

Cited by 58 publications

(26 citation statements)

References 6 publications

(7 reference statements)

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“…This is in agreement with our observation that the polynuclear species formed in the absence of iodide are entirely different [2] [3]. However, polynuclear ions with an empty Cu(1)-cube have also been synthesized and characterized structurally [6]. It is interesting to note that in one case 141 the halogen centered polynuclear species is found in a cubic s p c c group (F 432) with crystallographic threefold symmetry ( 3 ) , in the other [5] the space group is C2/c with crystallographic twofold symmetry (2) of the polynuclear ion, whereas in the present case the space group is Pi with no symmetry of tlie polynuclear ion.…”

supporting

confidence: 90%

“…0.3295 (10) 0.1524 ( 8 ) iI..5109 ( 0 ) 0.2303 (7) 0.1352 (7) -0.263.5 (8) -0.2312 (7) -~ 0.4669 (7) 0.2965 (6) -0.3730 (7) --0 . 4 l l L (0) --0.1796 (6) 0.4420 (8) 0.2988 (10) 0.4973 (8) 0.14711 (8, 0.2265 (6) wcalr reflcctions was applied. :\bout 150 small E-values were sc,lcctcd according to the criterion B . '…”

Section: Experimental Partmentioning

confidence: 99%

“…cd (6)-1(1) 3.501 (6) .i 2.918 (6) 2.51 (1) 2.52 ( 2 ) 3.078 (7) 2.53 (2) 2.51 (5) 2.55 (2) 2 52 (2) 2.52 (1) 3.665 (6) 2.893 (6) 2.54 (2) 2.54 (2) 2.47 (1) Cd (7) Results. --Positional and thermal parameters ol the Cd, I and S atoms are given in Table 1, those of C and 0 in Table 2.…”

Section: Experimental Partmentioning

confidence: 99%

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Stereochemistry of Polynuclear Cadmium(II) Thioglycolates: Crystal structure of cadmium(II) bisthioglycolate

Bürgi

1974

Helvetica Chimica Acta

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Eight Cd(II) ions arc found a t the corners of a distorted cubc, the centcr c i i 1111: cube is occupied by an iodidc, the twclvc thioglycolatc sulfur atonis bridge the twelve edges of the cube thereby forming a distorted icosahcdron. Cadmium ions arc cithcr five or seven coordinate. The phase problcin for this structure was solvcd using a combination of very high mil very lo^ B-values.Polynuclear cadmium thioglycolate compounds have been investigated both in solution J] and in the solid state [Zl [3]. A decanuclear ion of coi~iposition Cd,,Lf$ (L = HOCHzCHzS-) was identified by equilibrium studies ' 1; and its structure determined by crystallographic methods 13;. The arrangement of Cd-and S-atoms may be related to the sphalerite lattice.

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supporting

confidence: 90%

Section: Experimental Partmentioning

confidence: 99%

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Stereochemistry of Polynuclear Cadmium(II) Thioglycolates: Crystal structure of cadmium(II) bisthioglycolate

Bürgi

1974

Helvetica Chimica Acta

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“…The long Cu-(/18-S) contacts measured in this species, 2.694 X, suggest that the copper-sulfur bonding is somewhat ionic in character, as confirmed by Fenske-Hall MO calculations which indicate a highly negatively charged interstitial S atom [51]. The long Cu-Cu separations, 3.105 .&, are considerably longer than the Cu-Cu distances measured in the non-centered 128-MVE copper Cu8S~2 species (see above) [32][33][34]. Despite these long distances which might indicate no M-M bonding in this cluster, the Cu atoms do not obey the 16-electron rule, nor the 18-electron rule.…”

Section: Other Main Group Atom-centered Cubic Speciessupporting

confidence: 53%

Electron count versus structural arrangement in clusters based on a cubic transition metal core with bridging main group elements

Halet

Saillard

Structural and Electronic Paradigms in Cluster Chemistry

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The bonding of diverse molecular clusters based on a cubic transition metal core with bridging main group elements is reviewed. It is shown that the cluster topology of these compounds is dependent on several parameters which can be calibrated. A large range of electron counts is generally observed without alteration of the cubic architecture. Examination of their electronic structures indicates that these species are at the borderline between molecular and solid states, characterized either by a closed-shell electronic configuration secured by a significant HOMO-LUMO gap, or by a quasi-continuous energy level structure often associated with open-shell electronic configurations.

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“…Calcd for 1985, 24, 1258. (13) The highly insoluble complex that is formed by the reaction of (nBu4N),Re2Br8 with dppm in refluxing acetonitrile and which we had originally formulated as "a-[ReBr,(dppm)],,'4 is in reality [Re,Br,(pdpp~n),(NCMe)~]Br. It undergoes anion exchange with PF6-to afford [Re~Br,(r-dppm)2(NCMe)21 PF6.…”

Section: A Reactions Of [Re2x3(p-dppm)2(ncr)2]pf6 (X = CI Br; R = Mmentioning

confidence: 99%

Redox reactions of the dirhenium(II) complexes Re2X4(dppm)2 (X = Cl, Br; dppm = Ph2PCH2PPh2). The reductive coupling of nitriles with retention of a metal-metal-bonded dirhenium unit

Esjornson¹,

Derringer²,

Fanwick³

et al. 1989

Inorg. Chem.

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ChemInform Abstract Dirhenium(II) complexes such as (I) react with acetonitrile (II) to give the paramagnetic compounds (III), containing the coupling product of two acetonitriles as a new ligand. From the crystal structure determinations of (IIIb) (with (PF6)0.8 and Br0.2 as the counterions) and, still better, of (VI), both crystallizing in P1 with Z=2, it is concluded that the singly deprotonated diimine form of the ligand predominates although contributions of the triply deprotonated ene-diamine form are also present. The generality of the formation of (III) is demonstrated by isolation of analogous products arising from the coupling of EtCN, iPrCN, tBuCN and PhCN. The lability of the nitrile ligands is shown by the formation of (V). Experiments with CD3CN show the nitrile itself to be the source of hydrogen. Complexes (III) are readily oxidized by NOPF6 in CH2Cl2 or by ferricenium hexafluorophosphate in acetone to give the corresponding dications, which display well-defined 1H and 31P NMR spectra. (VI) is obtained in an attempt to grow crystals from (V), the way how one of the methyl groups is oxidized is unkown.

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Crystallographic evidence for copper-copper bonding at 2.8 Ang. Crystal and molecular structure of tetrakis(tetraphenylphosphonium) hexakis(1,2-dithiosquarato)octacuprate(I)

Cited by 58 publications

References 6 publications

Stereochemistry of Polynuclear Cadmium(II) Thioglycolates: Crystal structure of cadmium(II) bisthioglycolate

Stereochemistry of Polynuclear Cadmium(II) Thioglycolates: Crystal structure of cadmium(II) bisthioglycolate

Electron count versus structural arrangement in clusters based on a cubic transition metal core with bridging main group elements

Redox reactions of the dirhenium(II) complexes Re2X4(dppm)2 (X = Cl, Br; dppm = Ph2PCH2PPh2). The reductive coupling of nitriles with retention of a metal-metal-bonded dirhenium unit

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