Structural diversity of homoleptic ethane-1,2-dithiolato complexes of the first transition series

Dorfman, Jay R.; Rao, Ch. Pulla; Holm, R. H.

doi:10.1021/ic00198a002

Cited by 43 publications

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“…The Cr–S distances are 2.2912(11) Å (Cr1–S1) and 2.3124(9) Å (Cr1–S2a), and the distance between chromium and the centroid of the flanking ring is 2.11477(6) Å. The Cr–S bond distances in 1 are slightly shorter than the Cr–S bond length of 2.3505(5) Å in Cr(SAr iPr 6 ) 2 or the average Cr–S bond length of 2.388 Å in [Cr(SCH 2 CH 2 S) 2 ][NMe 4 ] 2 . , Previously published data on the only known two-coordinate chromium thiolate Cr(SAr iPr 6 ) 2 revealed a crystallographically symmetrical structure that exhibits linear coordination at the metal atom . In addition, the ipso -carbon atoms of the central aryl rings of the terphenyl groups were found to form a coplanar array with the S–Cr–S unit.…”

Section: Resultsmentioning

confidence: 90%

“…Structures. The solid-state structures determined by singlecrystal X-ray diffraction of compounds 1−7 are illustrated in 79,80 Previously published data on the only known two-coordinate chromium thiolate Cr(SAr iPr 6 ) 2 revealed a crystallographically symmetrical structure that exhibits linear coordination at the metal atom. 35 In addition, the ipso-carbon atoms of the central aryl rings of the terphenyl groups were found to form a coplanar array with the S−Cr−S unit.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The Cr−S distances are 2.2912(11) Å (Cr1−S1) and 2.3124(9) Å (Cr1−S2a), and the distance between chromium and the centroid of the flanking ring is 2.11477(6) Å. The Cr−S bond distances in 1 are slightly shorter than the Cr−S bond length of 2.3505(5) Å in Cr(SAr iPr 6 ) 235 or the average Cr−S bond length of 2.388 Å in [Cr(SCH 2 CH 2 S) 2 ]-[NMe 4 ] 2 79,80. Previously published data on the only known two-coordinate chromium thiolate Cr(SAr iPr 6 ) 2 revealed a crystallographically symmetrical structure that exhibits linear coordination at the metal atom 35.…”

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Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes

et al. 2018

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The first-row transition-metal(II) dithiolates M(SAr) [Ar = CH-2,6-(CH-2,6-iPr); M = Cr (1), Mn (3), Fe (4), Co (5), Ni (6), and Zn (7)] and Cr(SAr) [2; Ar = CH-2,6-(CH-2,4,6-Me)] and the ligand-transfer reagent (NaSAr) (8) are described. In contrast to their M(SAr) (M = Cr, Mn, Fe, Co, Ni, and Zn; Ar = CH-2,6-(CH-2,4,6-iPr)) congeners, which differ from 1 and 3-6 in having p-isopropyl groups on the flanking aryl rings of the terphenyl substituents, compounds 1 and 4-6 display highly bent coordination geometries with S-M-S angles of 109.802(2)° (1), 120.2828(3)° (4), 91.730(3)° (5), and 92.68(2)° (6) as well as relatively close metal-flanking aryl ring η interactions with metal-centroid distances of 2.11477(6) Å (1), 1.97188(3) Å (2), 2.15269(6) Å (4), 1.62058(9) Å (5), and 1.724(8) Å (6). However, the d (Mn) and d (Zn) complexes 3 and 7 display linear or near-linear coordination with no close metal-ligand distances. The nonlinear geometries of 1 and 4-6 also contrast with those of their Ar-substituted alkoxo and amido congeners, which have strictly linear coordination. Complexes 1-7 were synthesized by the reaction of the lithium or sodium thiolate salt with the metal dihalide or, in the case of 3, by the reaction of the thiol with the amido complex Mn[N(SiMe)]. All compounds were characterized by electronic spectroscopy, X-ray crystallography, and magnetic measurements using Evans' method and SQUID magnetometry. It was concluded that, despite the large bulk of the Ar substituents, the absence of p-isopropyl groups on the flanking rings of the ligand permits close secondary metal-flanking ring distances. The compounds are characterized by more intense colors and display magnetic moments that are generally lower than the spin-only values, in agreement with the covalent character of the close metal-flanking ring η interactions.

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Section: Resultsmentioning

confidence: 90%

Section: ■ Results and Discussionmentioning

confidence: 99%

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confidence: 92%

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Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes

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“…This soluble species analyzes as (approximately) N(C4Hg)4CoS8 and gives an NMR signal which suggests that at least some of the cobalt is present as Co (III). It is too early in the investigation to determine whether the behavior is similar to that observed by Holm in cobalt ethanedithiolates (11).…”

Section: Resultsmentioning

confidence: 96%

Transition Metal Polysulfides as Battery Cathodes

Bowden¹,

Barnette²,

Demuth³

1988

J. Electrochem. Soc.

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Amorphous polysulfides of iron, nickel, and cobalt were prepared and characterized. The resulting compounds, Co2S7, Co2S9, Ni2ST, and Fe3Ss were evaluated as cathode materials in organic electrolyte lithium batteries. The cobalt compounds in particular delivered very high capacities of 1-1.2 A-h/g at voltages around 1.SV. The resulting cells possessed high gravimetric and volumetric energy densities.Sulfur is a very high energy density cathode for a lithium battery. Since elemental sulfur is an extremely good insulator, it has poor properties as an electrode. Sulfur is also soluble in some organic solvents, and tends to form polysulfides which are even more soluble in the presence of an alkali metal sulfide. Thus, sulfur does not appear to be an attractive candidate material for use in an organic electrolyte ambient temperature lithium battery. Metal sulfides with a fully reduced sulfur, such as FeS, do not utilize the high energy density of sulfur, since the sulfur does not participate in the overall reaction [1] 2Li+ FeS -~ Li2S + Fe[1]Earlier workers have tried to utilize the high energy densities of sulfur by using alkali metal polysulfides. In one case, the lithium polysulfides were dissolved in a THF based organic electrolyte and discharged at a porous carbon electrode, giving a rechargeable cathode (1). Since both polysulfide species were soluble, both high rate discharge and recharge were expected [2] Li2S4 + 2Li ~ 2Li~S~[2]In another, more recent approach, the alkali metal polysulfides were used in electrolytes in which the polysultides were insoluble. The resulting cells had a much longer storage life, but high current capabilities of the cells were limited (2). Both previous examples of polysulfide electrochemistry promised high gravimetric energy densities, but limitations on power capability and/or storage have, thus far, prevented commercial development of the systems. A composite approach is to combine the very high energy density of sulfur with the insolubility and good electrochemical behavior of a transition metal sulfide. An excellent example of such a compound, which combines both sulfur capacity and sulfide cathode characteristics, is iron pyrite, FeS2. The electrochemistry of iron pyrite has been studied and very high gravimetric and volumetric energy densities have been shown to be attainable (3). The discharge of FeS2 is a complex process, unlike the simplified form [3] shown below, although this appears to approximate the final products and stoichiometryThere are numerous examples of transition metal disulfides to choose from, such as COS2, NiS2, and MnS2, as well as FeS2. Metal trisulfides and higher sulfides are much less well known, with TiS3 and VS4 being the only *Electrochemical Society Active Member.well-known first row polysulfides and MoS3 and NbS3 in the second transition series. This is in substantial contrast to the alkali metals, where species such as Cs2S~ and Na2S5 are comparatively stable and well known. In view of the growing chemistry of polysulfide complexes fr...

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“…1. In this model, assigned number 1, steam is fed parallel (11) to the tube, and is progressively decomposed, at different segments, dx, along the tube; resulting in the mole fraction of hydrogen, N(H2)x increasing to its final exit value of N~H2~ ( dN(n2)xl_ V-Co…”

Section: Conceptual Modelmentioning

confidence: 99%

Performance Models for Zirconia Electrolyte Cells at Low Current Density

Maskalick

McLain

1988

J. Electrochem. Soc.

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This preliminary design study compares high temperature electrolysis, having H20(g) flow delivered parallel to the tube (model I), with H20(g) reactant cross-fed, perpendicular to the axes of series-connected tubes (model 2). Calculations for model 1 correlate with relevant experimental data. Model 2 calculations predict higher energy efficiencies than model i. If model 2 design philosophy is employed, hydrogen production is estimated, at 99.9% purity, and at i00 mA/cm ~, to require 1.017V at 0.902 energy efficiency, using tubular cells employing the present design. Tube design optimization, with normalized cell resistance, p lowered to 0.35 ~ cm 2, is estimated to result in 99.9% pure hydrogen product at 0.952V and 0.963 energy efficiency for the same i00 mAJcm 2 design point. Hydrogen purity, cell current density, and resistance are key modeling parameters.An electrical generator employing a low temperature trolyte (e.g., 1000~ will provide a net power output (Pnet) hydrogen-oxygen fuel cell in closed cycle with a high if sustaining solar thermal energy is available and cell temperature H20 electrolysis cell with solid oxide eleccurrent effieiencies, ~'f and ~'e are high. If V~ and Ve are, respectively, fuel cell and electrolysis cell driving volt-*Electrochemical Society Active Member. ages, then, at a current, I ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 130.179.16.201 Downloaded on 2015-06-14 to IP Vol. 135, No. 1 ZIRCONIA ELECTROLYTE CELLS 7 P.~t = [c~'fV~ -VJ~'~]I ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 130.179.16.201 Downloaded on 2015-06-14 to IP

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Structural diversity of homoleptic ethane-1,2-dithiolato complexes of the first transition series

Cited by 43 publications

References 0 publications

Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes

Effects of Remote Ligand Substituents on the Structures, Spectroscopic, and Magnetic Properties of Two-Coordinate Transition-Metal Thiolate Complexes

Transition Metal Polysulfides as Battery Cathodes

Performance Models for Zirconia Electrolyte Cells at Low Current Density

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