Illusive tungsten-imido-dithiocarbamate complexes: Facile carbon–nitrogen bond formation

Edwards, Alexander D.; Hogarth, Graeme; Hollingsworth, Nathan; Oller, Joseph J.

doi:10.1016/j.inoche.2011.09.014

Cited by 6 publications

(7 citation statements)

References 54 publications

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“…Dithiocarbamates form complexes with all of the transition elements and in a wide range of oxidation states [2] [19]. The ability of the dithiocarbamate ligand to stabilize both low-and high-valent metal ions is generally attributed to the adoption of dithiocarbamate and thioureide tautomers (Fig.…”

Section: Metal Complexes -Bondingmentioning

confidence: 99%

“…Sometimes the anisobidentate coordination is more debatable. For example in [W(N t Bu) 2 (S 2 CN i Bu 2 ) 2 ] the tungsten-sulfur bonds trans to the imide ligands [W-S(av) 2.707(1) Å] are significantly longer than those lying cis [W-S(av) 2.462(1) Å] but this is attributed to the trans-influence of the imide ligands rather than anisobidentate coordination [19] (Fig. 4).…”

Section: Binding Modesmentioning

confidence: 99%

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Metal-dithiocarbamate complexes: chemistry and biological activity

Hogarth¹

2012

MRMC

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Dithiocarbamates are highly versatile mono-anionic chelating ligands which form stable complexes with all the transition elements and also the majority of main group, lanthanide and actinide elements. They are easily prepared from primary or secondary amines and depending upon the nature of the cation can show good solubility in water or organic solvents. They are related to the thiuram disulfides by a one-electron redox process (followed by dimerisation via sulfur-sulfur bond formation) which is easily carried out upon addition of iodide or ferric salts. Dithiocarbamates are lipophilic and generally bind to metals in a symmetrical chelate fashion but examples of other coordination modes are known, the monodentate and anisobidentate modes being most prevalent. They are planar sterically non-demanding ligands which can be electronically tuned by judicious choice of substituents. They stabilize metals in a wide range of oxidation states, this being attributed to the existence of soft dithiocarbamate and hard thioureide resonance forms, the latter formally resulting from delocalization of the nitrogen lone pair onto the sulfurs, and consequently their complexes tend to have a rich electrochemistry. Tetraethyl thiuramdisulfide (disulfiram or antabuse) has been used as a drug since the 1950s but it is only recently that dithiocarbamate complexes have been explored within the medicinal domain. Over the past two decades anti-cancer activity has been noted for gold and copper complexes, technetium and copper complexes have been used in PET-imaging, dithiocarbamates have been used to treat acute cadmium poisoning and copper complexes also have been investigated as SOD inhibitors.

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Section: Metal Complexes -Bondingmentioning

confidence: 99%

Section: Binding Modesmentioning

confidence: 99%

Metal-dithiocarbamate complexes: chemistry and biological activity

Hogarth¹

2012

MRMC

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“…Cycloaddition to transition metal–nitrogen multiple bonds is a key transformation that has broad applications across organic synthesis, dinitrogen activation, polymerization, , and small molecule formation . This process can be more specifically applied to the synthesis of urea derivatives, which are fairly common based on the variety of κ 2 -ureato complexes of niobium, rhenium, ruthenium, , titanium, , tungsten, and zirconium synthesized via [2 + 2] cycloadditions of isocyanates. ,,,− …”

Section: Introductionmentioning

confidence: 99%

[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ²-Ureato Compounds

2017

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A new family of uranium(IV) imido complexes of the form Tp*U(NR) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate; R = benzyl (Bn), para-tolyl (p-Tol), 2,6-diethylphenyl (detp), and 2,6-diisopropylphenyl (dipp)) have been generated by bibenzyl extrusion from Tp*UBn. Tp*U(NBn), Tp*U(Np-Tol), and Tp*U(Ndetp), along with previously reported Tp*U(NPh) and Tp*U(NAd) (Ad = 1-adamantyl), readily undergo [2π+2π] cycloaddition with isocyanates and isothiocyanates to generate κ-ureato and κ-thioureato derivatives, respectively. These new uranium(IV) complexes were characterized via multinuclear NMR, vibrational and electronic absorption spectroscopies, and, where possible, X-ray crystallography. The steric demands of the ligands were quantitatively assessed using computational modeling, and it was shown that cycloaddition only occurs for imido species where ligands occupy 90% or less of the coordination sphere.

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“…77 Other sulphur-and nitrogen-containing compounds have been reported. [78][79][80][81][82][83][84][85] Phosphorus-donor ligands Reactions of R 2 P-P(SiMe 3 )Li (R = t Bu, i Pr, i Pr 2 N, Et 2 N) with [Cp 2 WCl 2 ] were reported to yield terminal phosphanylphosphido complexes [Cp(C 5 H 4 P-PR 2 )WH] or [Cp(C 5 H 4 P-PR 2 )W(SiMe 3 )] by way of a hydrogen or SiMe 3 migration to tungsten. 86 The solid-state structures of [Cp(C 5 H 4 P-P t Bu 2 )WH] and [Cp(C 5 H 4 P-PNEt 2 )WH] were solved by X-ray crystallography.…”

Section: Carbon-donor Ligandsmentioning

confidence: 99%

Chromium, molybdenum and tungsten

Holder

2012

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This chapter reviews the literature reported during 2011 on some important advances in the areas of catalysis, bioinorganic, and organometallic chemistry for the chromium triad. Research highlights for each metal during the year are also given. HighlightsThe highlights include: (I) The first four-membered planar metallacycles, containing an MRM triple bond, obtained in reaction with (Me 3 Si) 2 N-PQNSiMe 3 ; 1 (II) chromium(III)-containing species used in reducing cholesterol, triglycerides, and carbohydrate, and affecting lipid metabolism; 2-4 (III) a study used to evaluate the effect chromium picolinate on swine growth performance, meat quality, and protein deposition in skeletal muscle; 5 (IV) a report based on the structure, photophysics, electrochemistry, DFT calculation, and in vitro antioxidant activity of coumarin Schiff base complexes of group 6 metal carbonyls; 6 (V) a new class of photochemically activated CO-releasing molecules; 7 (VI) a new coordination polymer, H[(Ce(H 2 O) 5 ) 2 -(Ce(pdc) 2 (H 2 O) 4 )(Ce(pdc) 3 )(PW 12 O 40 )]Á2H 2 O, that was found to be active for photocatalytic H 2 evolution under UV irradiation.

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Illusive tungsten-imido-dithiocarbamate complexes: Facile carbon–nitrogen bond formation

Cited by 6 publications

References 54 publications

Metal-dithiocarbamate complexes: chemistry and biological activity

Metal-dithiocarbamate complexes: chemistry and biological activity

[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ²-Ureato Compounds

Chromium, molybdenum and tungsten

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Illusive tungsten-imido-dithiocarbamate complexes: Facile carbon–nitrogen bond formation

Cited by 6 publications

References 54 publications

Metal-dithiocarbamate complexes: chemistry and biological activity

Metal-dithiocarbamate complexes: chemistry and biological activity

[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ2-Ureato Compounds

Chromium, molybdenum and tungsten

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[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ²-Ureato Compounds