40 years of transition-metal thiocarbonyl chemistry and the related CSe and CTe compounds

Petz, Wolfgang

doi:10.1016/j.ccr.2007.12.011

Cited by 59 publications

(32 citation statements)

References 111 publications

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“…Some comparison with dissociation energies for the corresponding Fe 4 (CO) n+4 derivatives is also presented in Table 1. The experimental carbonyl dissociation energies for Ni(CO) 4 , Fe(CO) 5 , and Cr(CO) 6 are 27, 41, and 37 kcal/mol, respectively. [45] The data in Table 1 suggest major differences between the chemistry of Fe 4 (CS) 4 (CO) n and the corresponding Fe 4 (CO) n+4 derivatives.…”

Section: Thermochemistrymentioning

confidence: 94%

“…In addition, the two Fe 4 (CS) 4 (CO) 12 structures 12-4 and 12-5 with a central Fe 4 rhombus and two symmetric bridging CS groups are found at the relatively high energies of at least 19(17) kcal/mol above 12-1 ( Figure 4 and Table S1). These two structures can be generated by the replacement of the bridging CO group in the binuclear Fe 2 (μ-CS) 2 (μ-CO)-(CO) 6 structure [9] with an unbridged Fe 2 (CS) 2 (CO) 6 fragment. The doubly bridged Fe2-Fe3 bond lengths in these two structures are predicted to be ca.…”

Section: Fe 4 (Cs) 4 (Co)mentioning

confidence: 99%

“…A number of metal thiocarbonyl derivatives have been synthesized in which one or more carbonyl groups of a wellknown homoleptic metal carbonyl have been replaced by a thiocarbonyl group. [5,6] These include M(CS)(CO) 5 (M = Cr, Mo, W), [7] which is isoelectronic with M(CO) 6 , and Fe(CS)(CO) 4 , [8] which is isoelectronic with Fe(CO) 5 . However, polynuclear metal derivatives that contain only CO and CS ligands have not yet been synthesized.…”

Section: Introductionmentioning

confidence: 99%

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New Structural Features in Tetranuclear Iron Carbonyl Thiocarbonyls: Exotriangular Iron Atoms and Six‐Electron‐Donating Thiocarbonyl Groups Bridging Four Iron Atoms

Zhang

King

et al. 2012

Eur J Inorg Chem

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DFT led to the discovery of two new structural motifs in tetranuclear iron carbonyl thiocarbonyls, Fe4(CS)4(CO)n (n = 12, 11, 10, 9), which are not found in their homoleptic analogues, Fe4(CO)n+4. Thus the lowest energy Fe4(CS)4(CO)12 structures have a central Fe3 triangle with an exotriangular iron atom joined to the Fe3 triangle through a four‐electron donor CS bridge. This contrasts with the structure of Os4(CO)16 and the predicted structure of Fe4(CO)16, which consist of an M4 rhombus and two‐electron donor carbonyl groups. An even more remarkable new structural motif for the Fe4(CS)4(CO)n derivatives is the irregular Fe4 “rhombus” (actually a trapezium) bridged by a six‐electron donor η2‐μ4‐CS group. This type of structure is found in the lowest energy structures of both Fe4(CS)4(CO)10 and Fe4(CS)4(CO)9 and makes Fe4(CS)4(CO)10 viable enough to be a promising synthetic objective. On the contrary, Fe4(CS)4(CO)11 is found to be thermochemically unfavorable both with respect to CO dissociation and disproportionation into Fe4(CS)4(CO)12 and Fe4(CS)4(CO)10.

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Section: Thermochemistrymentioning

confidence: 94%

Section: Fe 4 (Cs) 4 (Co)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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New Structural Features in Tetranuclear Iron Carbonyl Thiocarbonyls: Exotriangular Iron Atoms and Six‐Electron‐Donating Thiocarbonyl Groups Bridging Four Iron Atoms

Zhang

King

et al. 2012

Eur J Inorg Chem

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“…[3,7] Until now, C 2 S 2 , generated by flash vacuum pyrolysis, has been either detected by neutralization reionization mass spectrometry [8] or isolated in an argon matrix and characterized by combination of IR and UV spectroscopy and ab initio calculations. [7,9] While small elusive sulfur species, such as SO, [10] NS, [10d, 11] PS, [12] or S 2 À , [13] could be stabilized by coordination, and CS complexes are wellestablished, [5,14] C 2 S 2 complexes are unknown to date. In the course of our work on acetylenedithiolate (acdt 2À ) complexes, [15] we were now able to generate ethenedithione in a dinuclear cobalt complex that is stable at ambient temperature.…”

Section: Dedicated To Professor Gerhard Erker On the Occasion Of His mentioning

confidence: 99%

Ethenedithione (SCCS): Trapping and Isomerization in a Cobalt Complex

et al. 2011

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Swing bridge: The triplet species ethenedithione has been generated within the coordination sphere of cobalt, leading to a dinuclear μ-η(2)-η(2)-C(2)S(2) complex (see picture: C gray, Co blue, P purple, S yellow). Depending on the solvent, the C(2)S(2) moiety displays a transoid or a cisoid geometry. This isomerization step changes the sign of the magnetic coupling between the cobalt centers.

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“…Because of the instability of carbon monosulfide, indirect methods must be used to introduce thiocarbonyl groups into transition metal complexes, using compounds such as carbon disulfide (CS 2 ) or thiophosgene (S=CCl 2 ) as sources of CS groups. [12][13][14][15][16] The stability of the [(η 5 -C 5 H 5 )MnL 3 ] system allows the entire series of cyclopentadienylmanganese carbonyl thiocarbonyls [(η 5 -C 5 H 5 )Mn(CS) n (CO) 3-n ] (n = 1, 2, 3) to be synthesized. [17,18] Thus the mononuclear mono(thiocarbonyl) [ Because of the difficulty of synthesizing metal thiocarbonyls as compared with similar metal carbonyls, theoretical studies on metal thiocarbonyl chemistry are important for predicting the potential most productive areas of metal thiocarbonyl chemistry in order to focus synthetic studies on the most interesting targets.…”

Section: Introductionmentioning

confidence: 99%

Binuclear Cyclopentadienylmanganese Carbonyl Thiocarbonyls: Four‐Electron Donor Bridging Thiocarbonyl Groups of Two Types and a Bridging Acetylenedithiolate Ligand

Zhang

Xie

et al. 2010

Eur J Inorg Chem

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As a starting point, the mononuclear cyclopentadienylmanganese carbonyl thiocarbonyls [CpMn(CS)(CO)n] (Cp = η5‐C5H5; n = 2, 1, 0) and binuclear derivatives [Cp2Mn2(CS)2(CO)n] (n = 3, 2, 1, 0) have been studied by density functional theory (DFT). For coordinately saturated binuclear [Cp2Mn2(CS)2(CO)3], the four electron donor end‐on CE(E = O, S) bridged structures are preferred energetically over the normal CE (E = O, S) bridged structures, analogous to [Cr2(CS)2(CO)9]. The lowest energy structure for [Cp2Mn2(CS)2(CO)2] has one four‐electron donor bridging η2‐μ‐CS group. However, this structure is thermodynamically unstable with respect to disproportionation into [Cp2Mn2(CS)2(CO)3] and [Cp2Mn2(CS)2(CO)]. Only two structures are found for [Cp2Mn2(CS)2(CO)] as is the case for the carbonyl analogue [Cp2Mn2(CO)3]. The global minimum of [Cp2Mn2(CS)2(CO)], a singlet triply bridged structure, is very favorable energetically with respect to loss of a CO group, disproportionation into [Cp2Mn2(CS)2(CO)2] + [(Cp)2Mn2(CS)2], and dissociation into mononuclear fragments. The lowest energy structure for [Cp2Mn2(CS)2] is a triplet structure with two bridging CS groups and the Mn≡Mn triple bond required to give each Mn atom a 17‐electron configuration for a binuclear triplet. A higher energy singlet [Cp2Mn2(CS)2] structure is found with a very short MnblablaMn distance of about 2.1 Å suggesting the formal quadruple bond required to give each Mn atom the favored 18‐electron configuration. In other higher energy singlet and triplet [Cp2Mn2(CS)2] structures the two CS ligands have coupled to form an acetylenedithiolate ligand bridging the two manganese atoms.

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40 years of transition-metal thiocarbonyl chemistry and the related CSe and CTe compounds

Cited by 59 publications

References 111 publications

New Structural Features in Tetranuclear Iron Carbonyl Thiocarbonyls: Exotriangular Iron Atoms and Six‐Electron‐Donating Thiocarbonyl Groups Bridging Four Iron Atoms

New Structural Features in Tetranuclear Iron Carbonyl Thiocarbonyls: Exotriangular Iron Atoms and Six‐Electron‐Donating Thiocarbonyl Groups Bridging Four Iron Atoms

Ethenedithione (SCCS): Trapping and Isomerization in a Cobalt Complex

Binuclear Cyclopentadienylmanganese Carbonyl Thiocarbonyls: Four‐Electron Donor Bridging Thiocarbonyl Groups of Two Types and a Bridging Acetylenedithiolate Ligand

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