Conversion of a dithiocarbamate ligand to a thiocarboxamido ligand to form W(S)(PhC.tplbond.CPh)(S2CNEt2)(SCNEt2)

Brower, Douglas C.; Tonker, T. L.; Morrow, Janet R.; Rivers, David S.; Templeton, Joseph L.

doi:10.1021/om00137a005

Cited by 29 publications

(16 citation statements)

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“…Cleavage of both C−S bonds of the ligand was reported for reactions with [Ru 3 (CO) 12 ]2h and [Mo 2 ( μ ‐O 2 CMe) 4 ] 3. Other reactions of the dithiocarbamate ligand include oxidative addition of a C−S bond to alkynes4 and coupling reactions with coordinated alkyne,2c, 5 alkylidene,6 vinylidene/allenylidene,7 and cyanide8 ligands. Most of these studies involved Mo and W complexes, except for a few examples containing Cu,4d Nb and Ta,2g and Ru 2h, 7.…”

Section: Methodsmentioning

confidence: 98%

“…Although generally unreactive in the majority of its complexes, this ligand can undergo C−S bond cleavage, a phenomenon first observed in a Mo complex in 1972 and becoming increasingly common in the last two decades 2. In most cases, the cleaved S atom takes on a distinctly different coordination role in the complex, except where it is abstracted by an S acceptor such as PEt 3 2c. For example, the cleaved S atom can assume a bridging mode (M‐S‐M),2a,2b,2f, 3 form an M=S bond,2d,2g or interact with a neighboring ligand (e.g., the M≡C bond of a coordinated alkyne) 2e.…”

Section: Methodsmentioning

confidence: 99%

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C−S Bond Cleavage and C−C Coupling in Cyclopentadienylchromium Complexes To Give the First Dithiooxamide-Bridged and Doubly Dithiocarbamate-Bridged Double Cubanes: [Cp6Cr8S8{(C(S)NEt2)2}] and [Cp6Cr8S8(S2CNEt2)2]

et al. 2001

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There have been extensive studies on the use of the dithiocarbamate ligand in a variety of bonding modes for stabilizing a wide range of oxidation states in coordination compounds of main-group and transition metals. [1] Although generally unreactive in the majority of its complexes, this ligand can undergo CÀS bond cleavage, a phenomenon first observed in a Mo complex in 1972 and becoming increasingly common in the last two decades. [2] In most cases, the cleaved S atom takes on a distinctly different coordination role in the complex, except where it is abstracted by an S acceptor such as PEt 3 . [2c] For example, the cleaved S atom can assume a bridging mode (M-S-M), [2a,b,f, 3] form an MS bond, [2d,g] or interact with a neighboring ligand (e.g., the MC bond of a coordinated alkyne). [2e] Cleavage of both CÀS bonds of the ligand was reported for reactions with [Ru 3 (CO) 12 ] [2h] and [Mo 2 (m-O 2 CMe) 4 ]. [3] Other reactions of the dithiocarbamate ligand include oxidative addition of a C À S bond to alkynes [4] and coupling reactions with coordinated alkyne, [2c, 5] alkylidene, [6] vinylidene/allenylidene, [7] and cyanide [8] ligands. Most of these studies involved Mo and W complexes, except for a few examples containing Cu, [4d] Nb and Ta, [2g] and Ru. [2h, 7] In the course of our investigations on the reactivity of [{CpCr(CO) 3 } 2 ] (Cp h 5 -C 5 H 5 ) towards the EÀE bonds of organic substrates such as diphenyl dichalcogenides Ph 2 E 2 (E S, Se, Te), [9] and bis(diphenylthiophosphinyl)disulfane [Ph 2 P(S)S] 2 , [10] we studied reactions with tetraalkylthiuram disulfides [R 2 NC(S)S] 2 , and here we report the first organochromium complexes containing dithiocarbamate and dithiooxamide ligands.The instantaneous reaction of [{CpCr(CO) 3 } 2 ] with one molar equivalent of tetraethylthiuram disulfide [Et 2 NC(S)S] 2 in toluene at ambient temperature gave a dark red solution, which upon concentration yielded air-stable deep red crystals of [CpCr(CO) 2 (S 2 CNEt 2 )] (1) in 87 % yield. A similar reaction at 90 8C for 2 h gave a dark brown mixture, from which were obtained, in order of elution from a silica gel column, the following compounds: [{CpCr(CO) 2 } 2 S] (7) as a dark green solid (ca. 1 % yield), (1) (22 % yield), [CpCr(CO) 2 (SCNEt 2 )] (2) as a dark red crystalline solid (11 % yield), [Cp 4 Cr 4 S 4 ] (3) as a dark solid (22 % yield), [Cp 6 Cr 8 S 8 {(C(S)NEt 2 ) 2 }] (4) as a brown solid (6.8 % yield), suggests stable trap site for the hole, the position of which is not far from the acceptor. The slow recombination of the geminate ion pair with the relatively short distance would be related to the trap-site structure or some sorts of reorganizations because of the charge shift in the PVCz film.

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Section: Methodsmentioning

confidence: 98%

Section: Methodsmentioning

confidence: 99%

C−S Bond Cleavage and C−C Coupling in Cyclopentadienylchromium Complexes To Give the First Dithiooxamide-Bridged and Doubly Dithiocarbamate-Bridged Double Cubanes: [Cp6Cr8S8{(C(S)NEt2)2}] and [Cp6Cr8S8(S2CNEt2)2]

et al. 2001

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“…The evaluation of metal coordination complexes against various cytosolic targets were performed by our biochemistry research group (Atilim University, Ankara, Turkey) using the Pt(II) and Pd(II) complexes with diethyl dithiocarbamate [43] ligands (1 and 2, respectively), Pt(II) complexes with tris-(3) and bis-(4) substituted dimethyl sulfide (DMSO) [40], and Ni(II) complex with diethylxanthate [37] ligands, as shown in Fig. 2.…”

Section: Methodsmentioning

confidence: 99%

The role of metal coordination complexes in cytosolic cellular defense

Isgor

Özalp-Yaman

2013

Pure and Applied Chemistry

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The metal coordination complexes are known to induce cytotoxic effects on various cell lines and shown to have great potential for therapeutic interventions. Their main mechanism of action is through the mediation of enzyme activities in signaling pathways essential for cellular functioning. The overall cellular responses are dose-dependent and require high exposure levels and duration to overcome cellular defense against external toxicants. However, their effect through signal transduction components is limited due to the conferred drug resistance associated with glutathione transferase (GST)-mediated mechanisms. The GST family of enzymes is not only related to anticancer drug resistance, but also associated with cancer development where they may also contribute kinase signaling events including non-receptor protein tyrosine kinase (PTK)-related pathways. In the current study, we evaluated the effect of symmetrical and mononuclear complexes of Pd(II), Pt(II), and Ni(II) with organic ligands on cytosolic targets involved in glutathione utilization, antioxidant defense, and kinase signaling by virtue of acellular in vitro analyses.

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“…These sulfur based ligands have been used to model the active sites of some Mo/W containing enzymes, such as acetylene hydratase [5,13], but they are not without their drawbacks. The sulfur atoms are prone to redox chemistry and C-S bond cleavage reactions, which limit the utility of the compounds [14][15][16][17][18][19][20][21][22]. Moving to an oxygen based chelate will eliminate these undesirable side reactions and stabilize the metal with stronger field oxygen donor atoms.…”

Section: Introductionmentioning

confidence: 99%