96042-55-6

Upstream product

• 10199-34-5 bis(triphenylphosphine)platinum(II) dichloride 
• 68494-09-7 4,5-bis(benzoylthio)-1,3-dithiole-2-one 
• 10199-34-5 cis-dichlorobis(triphenylphosphine)platinum(II) 
• 68494-08-6 4,5-bis(benzoylthio)-1,3-dithiole-2-thione 
• 221296-23-7 cesium 4-(methylthio)-2-thioxo-1,3-dithiole-5-thiolate 

Relevant academic research and scientific papers

Experimental and theoretical studies on the mechanism of the C-S bond activation of PdII thiolate/thioether complexes

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).

Platinum(II) complexes bearing a thiolate/thioether ligand - Hemilability vs. dealkylation

Substitution of the chloro ligands of cis-[Pt(PEt3) 2Cl2] by 4-methylthio-2-thioxo-1,3-dithiole-5-thiolate (L) leads to the thiolato complexes trans-[Pt(PEt3)2ClL] (2) and trans-[Pt(PEt3)2L2] (1), which have been characterised by X-ray crystallography. In the solid state, the square planar arrangement is capped by an endocyclic sulfur atom of L, which gives rise to distorted square-pyramidal and pseudooctahedral geometries for 2 and 1, respectively. Complex 1 coexists in solution with [Pt(PEt3) (η1-L)(η2-L)] (3), which results from the reversible dissociation of one phosphane ligand. The combination of η1-(thiolato) and η2-(thiolato/thioether) L in 3 has been established by variable-temperature 1H NMR spectroscopy and crystal structure determination. The η2-coordination mode of L is also observed in cis-[Pt(PEt3)2L]+ (4), which results from the abstraction of the chloro ligand of 2 by excess TlPF 6. An S-demethylation reaction occurs when 1 is heated in acetonitrile to yield the structurally-characterised dithiolene complex [Pt(PEt3)2(dmit)] (5) (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate) and MeL. Treatment of cis-[Pt(PPh 3)2Cl2] with 2 equiv. of L leads to a mixture of [Pt(PPh3)2(dmit)] (6) and [Pt(PPh3) (η1-L)(η2-L)] (7). Complex 7 predominates in solution over its parent compound,[Pt(PPh3)2L 2]. The identification of CH3Cl by 1H NMR spectroscopy proves that [Pt(PPh3)2ClL] is involved as an intermediate in the demethylation process. The reaction of L with platinum precursors that are blocked in a cis arrangement by chelation of 1,1-bis(diphenylphosphanyl)methane (dppm) and 1,1-bis(diphenylphosphanyl)ethane (dppe) leads to the formation of the thiolato complexes cis- [Pt(η2-dppm)L2] (8) and cis-[Pt(η2- dppe)L2] (9). The solid-state structure of 8 reveals the occurrence of an additional weak interaction between a thiomethyl group and the platinum centre (Pt-S 3.073 A). Copyright

The synthesis and characterization of platinum monodithiolene complexes containing 1,3-dithiole-2-oxo-4,5-dithiolate (dmid2-) and 1,3-dithiole-2-thione-4,5-dithiolate (dmit2-)

The platinum monodithiolene complexes (COD)Pt(dmid) (1), (COD)Pt(dmit) (2), (Ph3P)2Pt(dmid) (3) and (Ph3P)2Pt(dmit) (4) (where COD=1,5-cyclooctadiene, dmid=1,3-dithiole-2-oxo-4,5-dithiolate, dmit=1,3-dithiole-2-thione-4,5-dithiolate) have been synthesized and characterized. We report here their 1H NMR, 195Pt NMR, UV-Vis spectra and electrochemistry. The X-ray crystal structures are also reported. 2: orthorhombic, Cmcm, a=10.8535(6), b=16.8503(7), c=7.3622(3) A, Z=4. 3: triclinic, P1, a=11.2051(4), b=11.4409(5), c=15.2212(9) A, α=71.882(4), β=73.125(4), γ= 84.589(6)°, Z=2. 4·CHCl3: triclinic, P1, a=10.2521(5), b=13.9387(14), c=15.6884(18) A, α=67.154(9), β=89.380(15), γ=83.570(13)°, Z=2. The crystal structure of 2 exhibits a molecular stacking pattern which has alternating Pt and S(thione) atoms forming a one-dimensional chain which suggests the presence of a weak axial interaction between the Pt and S(thione). A correlation exists between the 195Pt NMR chemical shifts and the one-electron oxidation potentials of these complexes. In addition, it is shown that the carbonyl of the dmid2- ligand is not susceptible to alkoxide attack when coordinated to platinum.