Oxidative addition of bis-(dimethoxybenzo)-1,2,5,6-tetrathiocins to Pt(PPh3)4: Synthesis and structures of mono- and di-metallic platinum dithiolate complexes, (dmobdt)Pt(PPh3)2 and [(dmobdt)Pt(PPh3)]2

Wrixon, Justin D.; Ahmed, Zeinab S.; Anwar, Muhammad U.; Beldjoudi, Yassine; Hamidouche, Nabila; Hayward, John; Rawson, Jeremy M.

doi:10.1016/j.poly.2015.09.049

Cited by 5 publications

(9 citation statements)

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“…It is noteworthy that dissociation of one M–P bond in complexes 1 , 2 , and 4 is induced by an intramolecular interaction between a thiomethyl group and the metal. For M P 2 (dithiolene) complexes, such phosphine dissociation is sometimes observed but intermolecular M···S interactions generating dimetallic species [M P (μ-dithiolene)] 2 appear to be the driving force in this case …”

Section: Resultssupporting

confidence: 59%

Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of Pd^II Thiolate/Thioether Complexes

et al. 2017

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Two equivalents of L (L = 4-methylthio-2-thioxo-1,3-dithiole-5-thiolate or Medmit) react with cis-Pd(PR3)2Cl2 (R = Ph and Et) to afford Pd(PR3)(η1-L)(η2-L) (R = Et: 1 ; R = Ph: 2) complexes, which have been characterized by X-ray crystallography. These compounds are dynamic in solution due to an exchange of the thiomethyl groups on palladium. Variable-temperature 1H NMR spectroscopy reveals a low coalescence temperature (173 K). Treatment of Pd(diphos)Cl2 (diphos = dppe or dppm) with 2 equiv of L affords thiolato complexes Pd(dppe)(η1-L)2 (3) and Pd(dppm)(η1-L)2 (4). Whereas 3 is rigid in solution with firm η2-coordination of dppe and η1-coordination of the thiolate, two linkage isomers Pd(η2-dppm)(η1-L)2 and Pd(η1-dppm)(η1-L)(η2-L) coexist in a solution of 4. L coordinated on PdII undergoes a S-demethylation reaction leading to dithiolene complexes and MeL. This transformation requires high temperature, and its efficiency depends on the nature of the phosphines as well as the nature of the metal (Pd vs Pt). DFT calculations reveal that the most likely mechanism depends on the lability of phosphines. Starting from M(PR3)2(η1-L)2 (M= Pd and Pt; R = Ph and Et), the favored sequence implies decoordination of one triethyl phosphine (M(PEt3)(η1-L)(η2-L)2 as intermediate) or two triphenylphosphines (Pd(η2-L)2 as intermediate) followed by oxidative addition and reductive elimination (OA/RE) reactions. In the case of PEt3, this OA/RE sequence can also compete with an intramolecular nucleophilic addition ( AN ), which can be described as an attack of a thiolate sulfur atom on a CH3 + carbocation. An intramolecular SN2 process was found to be the most feasible, starting from M(dppe)(η1-L)2 (M= Pd and Pt), with the nucleophile approaching the thiomethyl group at an angle of 180° with respect to the CCH3 –S bond. The influence of the coligand has also been studied experimentally. Structurally characterized disulfide L–L dimer has been isolated upon reaction of 2 equiv of L with MCl2 (M = Pd and Pt).

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Section: Resultssupporting

confidence: 59%

Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of Pd^II Thiolate/Thioether Complexes

et al. 2017

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“…In this context, it is worth noting that the 1 H NMR spectra of the dimeric group 10 complexes [M(dmobdt)(PPh 3 )] 2 (M = Pd and Pt; dmobdt 2− = dimethoxybenzenedithiolate) reveal two distinct chemical environments for the aromatic 1 H nuclei of the dmobdt 2− ligand. 21 DFT Studies. DFT studies on 3 were undertaken using the both B3LYP-D3 and M06 functionals and the LACV3P basis set augmented with diffuse and polarization functions for all atoms.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…1 H NMR studies on both 3 and 4 in CDCl 3 reveal the aryl protons to be equivalent, consistent with the presence of a 16 e – monomeric cyclopentadienyl cobalt dithiolate complex in solution rather than the 18 e – dimer. In this context, it is worth noting that the 1 H NMR spectra of the dimeric group 10 complexes [M(dmobdt)(PPh 3 )] 2 (M = Pd and Pt; dmobdt 2– = dimethoxybenzenedithiolate) reveal two distinct chemical environments for the aromatic 1 H nuclei of the dmobdt 2– ligand …”

Section: Results and Discussionmentioning

confidence: 99%

“…Their synthetic method is lengthy, and several intermediates were incompletely characterized and/or yields not reported. , An alternative synthetic strategy to access dithiolate complexes is the oxidative addition of dithietes to low-valent metals . This methodology has recently been exploited by Fekl and Kuropatov who examined oxidative addition of dithietes to Pd(0). , In this context, we have explored the related benzo-fused1,2,5,6-tetrathiocins which can be considered as dimers of the dithiete moiety and exhibit similar reactivity to zero-valent group 10 metal complexes. − …”

Section: Introductionmentioning

confidence: 99%

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Oxidative addition of 1,2,5,6-Tetrathiocins to Co(I): A Re-Examination of Crown Ether Functionalized Benzene Dithiolate Cobalt(III) Complexes

et al. 2022

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Oxidative addition of the 4′,4″,5′,5″-crown-functionalized dibenzo-1,2,5,6-tetrathiocins, [(OCH 2 CH 2 ) n OC 6 H 2 S 2 ] 2 (1, n = 4; 2, n = 5), to the Co(I) complex CpCo(CO) 2 under microwave irradiation in toluene affords 16e − Co(III) dithiolate complexes CpCo{S 2 C 6 H 2 O(CH 2 CH 2 O) n } 3 (n = 4) and 4 (n = 5) in 71−75% recovered yield. Complexes 3 and 4 were characterized by X-ray diffraction. Compound 3 was found to be polymorphic, crystallizing as the 16e − monomer, 3, or the 18e − dimer, (3) 2 , depending upon reaction conditions. In contrast to previous literature which suggested formation of 1:1 complexes between 3 and s-block cations, reaction of 3 with the s-block metal salts M[BPh 4 ] (M = Na, K, Rb, and Cs) formed the 2:1 complexes [{CpCo(S 2 C 6 H 2 O-(CH 2 CH 2 O) 4 )} 2 M][BPh 4 ] (5a−5d, respectively) whose structures were determined by X-ray diffraction and revealed that the alkali metal ion is sandwiched by two crown ether substituents in all cases. UV/vis titration studies of complex 3 with NaBPh 4 were consistent with formation of the 2:1 complex as the dominant species in solution. Mass spectrometry studies on 5a−5d revealed the presence of both [(3) 2 M] + and [(3)M] + ions (M = Na, K, Rb, and Cs). Electrochemical studies on 3 revealed an irreversible 1e − oxidation attributed to a ligand-based process based on DFT calculations. Chemical oxidation of 3 afforded two dimeric structures [{CpCo(S 2 C 6 H 2 O(CH 2 CH 2 O) 4 )} 2 ][X] 2 (6a, X = OTf; 6b, X = BF 4 ) in which dithiolate ligand oxidation leads to complexes containing a disulfide bond, consistent with electrochemical and computational studies.

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“…0.30 mmol) 5b: yield 0.097 g (44%). 1 13 C NMR (DMF-D 7 , δ, ppm, 75 MHz, 298 K): 160.9 (s, C-(2,4-dMOB)), 158.0 (s, C-(2,4-dMOB)), 154.5 (dd, 3 J C,P = 10.8 Hz, J C,P = 3.9 Hz, C-tazdt), 143.3 (dd, 3 J C,P = 12.3 Hz, J C,P = 3.7 Hz, C-tazdt), 133.9 (dd, 3 31 P NMR (DMF-D 7 , δ, ppm, 122 MHz, 298 K): 58.4 (d, 3 J P,P = 18.0 Hz, P-dppe), 56.1 (d, 3 J P,P = 18.0 Hz, P-dppe). MS (ESI-TOF, 9:1 MeOH:H 2 O with 0.1% HCOOH, m/z): 786 (M + H + ).…”

Section: General Synthesis Of the Metal Complexes 6 Andmentioning

confidence: 99%

Improved Synthesis and Coordination Behavior of 1H-1,2,3-Triazole-4,5-dithiolates (tazdt2−) with NiII, PdII, PtII and CoIII

2023

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A new synthetic route to 1H-1,2,3-triazole-4,5-dithiols (tazdtH2) as ligands for the coordination of NiII, PdII, PtII and CoIII via the dithiolate unit is presented. Different N-protective groups were introduced with the corresponding azide via a click-like copper-catalyzed azide-alkyne [3 + 2] cycloaddition (CuAAC) and fully characterized by NMR spectroscopy. Possible isomers were isolated and an alternative synthetic route was investigated and discussed. After removal of the benzyl protective groups on sulfur by in situ-generated sodium naphthalide, complexes at the [(dppe)M] (M = Ni, Pd, Pt), [(PPh3)2Pt] and [(η5-C5H5)Co] moieties were prepared and structurally characterized by XRD analysis. In this process, the by-products 11 and 12 as monothiolate derivatives were isolated and structurally characterized as well. With regioselective coordination via the dithiolate unit, the electronic influence of different metals or protective groups at N was investigated and compared spectroscopically by means of UV/Vis spectroscopy and cyclic voltammetry. Complex [(η5-C5H5)Co(5c)] (10), is subject to a dimerization equilibrium, which was investigated by temperature-dependent NMR and UV/Vis spectroscopy (solution and solid-state). The thermodynamic parameters of the monomer/dimer equilibrium were derived.

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Oxidative addition of bis-(dimethoxybenzo)-1,2,5,6-tetrathiocins to Pt(PPh3)4: Synthesis and structures of mono- and di-metallic platinum dithiolate complexes, (dmobdt)Pt(PPh3)2 and [(dmobdt)Pt(PPh3)]2

Cited by 5 publications

References 50 publications

Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of Pd^II Thiolate/Thioether Complexes

Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of Pd^II Thiolate/Thioether Complexes

Oxidative addition of 1,2,5,6-Tetrathiocins to Co(I): A Re-Examination of Crown Ether Functionalized Benzene Dithiolate Cobalt(III) Complexes

Improved Synthesis and Coordination Behavior of 1H-1,2,3-Triazole-4,5-dithiolates (tazdt2−) with NiII, PdII, PtII and CoIII

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Oxidative addition of bis-(dimethoxybenzo)-1,2,5,6-tetrathiocins to Pt(PPh3)4: Synthesis and structures of mono- and di-metallic platinum dithiolate complexes, (dmobdt)Pt(PPh3)2 and [(dmobdt)Pt(PPh3)]2

Cited by 5 publications

References 50 publications

Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of PdII Thiolate/Thioether Complexes

Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of PdII Thiolate/Thioether Complexes

Oxidative addition of 1,2,5,6-Tetrathiocins to Co(I): A Re-Examination of Crown Ether Functionalized Benzene Dithiolate Cobalt(III) Complexes

Improved Synthesis and Coordination Behavior of 1H-1,2,3-Triazole-4,5-dithiolates (tazdt2−) with NiII, PdII, PtII and CoIII

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Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of Pd^II Thiolate/Thioether Complexes

Experimental and Theoretical Studies on the Mechanism of the C–S Bond Activation of Pd^II Thiolate/Thioether Complexes