A novel route to dithiolenes from 1,3-dithiole-2-thiones at a dicobalt centre

Adams, Harry; Guio, Laurence V. Y.; Morris, Michael J.; Pratt, Andrew J.

doi:10.1039/b006052f

Cited by 4 publications

(7 citation statements)

References 5 publications

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“…Moreover, replacement of the bridging CO groups by bridging CS groups reduces the experimentally determined Co−Co distance of 2.528 Å in Co 2 (CO) 6 (μ-CO) 2 to the predicted Co−Co distance of 2.489 Å (B3LYP) or 2.497 Å (BP86) in Co 2 (CO) 6 (μ-CS) 2 ( 26 − 1 ). This is consistent with the experimentally determined CS bridged Co−Co distance of 2.449 Å in Co 2 (μ-CS)(μ-S 2 C 2 R 2 )(CO) 3 (μ-dppm).…”

Section: Resultssupporting

confidence: 91%

“…All of these seven structures were predicted to have only real harmonic vibrational frequencies. The global minimum for Co 2 (CS) 2 (CO) 6 , namely 26 − 1 , is a C 2 v structure Co 2 (μ-CS) 2 (CO) 6 with two bridging CS groups similar to the structure of Co 2 (CO) 8 characterized by X-ray diffraction. − The Co−C(S) and C−S distances of 26 − 1 are predicted to be ∼1.94 Å and ∼1.59 Å, respectively, with both methods, which are similar to the corresponding geometrical parameters of Co 2 (μ-CS)(μ-S 2 C 2 R 2 )(CO) 3 (μ-dppm) (1.912 Å and 1.609 Å), determined by X-ray diffraction . Moreover, replacement of the bridging CO groups by bridging CS groups reduces the experimentally determined Co−Co distance of 2.528 Å in Co 2 (CO) 6 (μ-CO) 2 to the predicted Co−Co distance of 2.489 Å (B3LYP) or 2.497 Å (BP86) in Co 2 (CO) 6 (μ-CS) 2 ( 26 − 1 ).…”

Section: Resultsmentioning

confidence: 62%

“…However, binuclear cobalt carbonyl thiocarbonyls with the general formula Co 2 (CS) n (CO) 8− n isoelectronic with Co 2 (CO) 8 remain unknown. Attempts to synthesize such cobalt carbonyl thiocarbonyls by the reaction of Co 2 (CO) 8 with CS 2 under various conditions gave complicated mixtures of products, most of which have structures built from stable tetrahedral Co 3 C or Co 3 S cluster units. − However, Morris and co-workers have synthesized and structurally characterized the related dithiolene cobalt thiocarbonyl phosphine complexes [Co 2 (μ-CS)(μ-S 2 C 2 R 2 )(CO) 3 (μ-dppm)] [R = CO 2 Me, CO 2 Et; dppm = (C 6 H 5 ) 2 PCH 2 P(C 6 H 5 ) 2 ] with a single bridging CS group. In addition, the binuclear cyclopentadienyliron carbonyl thiocarbonyl Cp 2 Fe 2 (μ-CS) 2 (CO) 2 has been synthesized , and shown by X-ray diffraction to containing two bridging thiocarbonyl groups in preference to bridging carbonyl groups.…”

Section: Introductionmentioning

confidence: 99%

“…thiocarbonyls by the reaction of Co 2 (CO) 8 with CS 2 under various conditions gave complicated mixtures of products, most of which have structures built from stable tetrahedral Co 3 C or Co 3 S cluster units. [15][16][17][18][19][20][21] However, Morris and coworkers 22 have synthesized and structurally characterized the related dithiolene cobalt thiocarbonyl phosphine complexes…”

Section: Introductionmentioning

confidence: 99%

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Binuclear Cobalt Thiocarbonyl Carbonyl Derivatives: Comparison with Homoleptic Binuclear Cobalt Carbonyls

Zhang

Xie

et al. 2009

Inorg. Chem.

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Density functional theory studies on Co(2)(CS)(2)(CO)(8) show the structure with two bridging CS groups to be the global minimum. Furthermore, swapping a terminal CO group with a bridging CS group to give a terminal CS group and a bridging CO group increases the energy of the structure by 7 +/- 2 kcal/mol. Thus, unbridged Co(2)(CS)(2)(CO)(8) structures lie at least 11 kcal/mol above the doubly bridged global minimum Co(2)(mu-CS)(2)(CO)(6), unlike Co(2)(CO)(8) where the doubly bridged and unbridged structures are significantly closer in energy. The lowest energy unsaturated Co(2)(CS)(2)(CO)(n) (n = 5, 4, 3) structures are predicted to contain four-electron donor bridging eta(2)-mu-CS groups, unlike the corresponding homoleptic carbonyls Co(2)(CO)(n+2), which contain only two-electron donor carbonyl groups. For example, the three lowest energy Co(2)(CS)(2)(CO)(5) structures contain a single eta(2)-mu-CS group accompanied by a Co-Co distance of approximately 2.7 A, consistent with the single bond required to give both cobalt atoms the favored 18-electron configuration.

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Section: Resultssupporting

confidence: 91%

Section: Resultsmentioning

confidence: 62%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Binuclear Cobalt Thiocarbonyl Carbonyl Derivatives: Comparison with Homoleptic Binuclear Cobalt Carbonyls

Zhang

Xie

et al. 2009

Inorg. Chem.

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“…The BP86 results on the dicobalt carbonyl thiocarbonyl series Co 2 (CS) 2 (CO) n ( n = 6, 5, 4, 3) are given in Table . For Co 2 (CS) 2 (CO) 6 , minima S-1 and S-2 (different bridging ligands) have Co–Co single bonds, where the R MM value of 2.497 Å for S-1 is close to the experimental (Morris) single bond length of 2.449 Å in the complex Co 2 (μ-CS)(μ-S 2 C 2 R 2 )(CO) 3 (μ-dppm). The bridging thiocarbonyl ligands in S-1 have a MM bond shortening effect greater than that of the bridging CO ligands in Co 2 (CO) 8 .…”

Section: Cobalt–cobalt Bondsmentioning

confidence: 55%

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

2018

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This survey of metal–metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) n+, (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging. The combination of experimental and computational results leads us to propose for the first time the ranges and “best” estimates for MM bond distances of all types (Ti–Ti through Zn–Zn, single through quintuple).

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Applications in Coordination Chemistry

Nakamoto

2008

Infrared and Raman Spectra of Inorganic and Coordination Compounds

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A novel route to dithiolenes from 1,3-dithiole-2-thiones at a dicobalt centre

Cited by 4 publications

References 5 publications

Binuclear Cobalt Thiocarbonyl Carbonyl Derivatives: Comparison with Homoleptic Binuclear Cobalt Carbonyls

Binuclear Cobalt Thiocarbonyl Carbonyl Derivatives: Comparison with Homoleptic Binuclear Cobalt Carbonyls

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

Applications in Coordination Chemistry

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