ASEAN Synergy to Overcome Challenges in Investment Arbitration

Cambodia, Indonesia, Lao, Malaysia, Thailand, and the Philippines, have been sued by foreign investors through International investment arbitrations (IIA). No matter whether the outcome is favorable or not, those countries have spend significant time, energy, and financial resources to arbitrate. ASEAN countries are not in advantageous position in IIA.The first and the most obvious reason is language barrier. Arbitration proceedins are mainly conducted in English. Consequently, the arbitrators and counsels more often than not come from English speaking countries. Not only do they lead to high cost, but also they lack of familiarity with South East Asia\u27s social, politics, economic, culture and customs. This may influence how they treat the cases such as the interpretation of provisions specifically designed to protect foreign investors such as: national treatment; fair and equitable treatment; most favored nation; and also in deciding jurisdictional issues. regional news as a legal basis for foreign investment activities aim to provide protection for foreign investor. On the other hand, it also serves as a mean to facilitate economic development in the host states of investment. Unfortunately, BITs often contain excessive and limitless protection clauses in order to attract foreign investors. This may endanger host states position as it can be used as a weapon by the investors to sue the host states. In responding to this fact, it is necessary to strengthen cooperation among ASEAN members in dealing with foreign investors through BIT. The ideal picture will be that SEA is pro-market and pro-arbitration reform. It is unavoidable that in order to protect themselves from harsh investors as well as intricate arbitration, ASEAN would be better off having its own investment arbitration center run by its experts. Thus, the short-term challenge is to equip legal practitioners, business players and academicians with more knowledge, skills and experiences in dealing with investment disputes. The long-term step will be to negotiate model of investment treaties applicable in the region and to harmonize national investment laws. These efforts are strategic opportunities for ASEAN as single market to keep balance between promoting investment, protecting investors and the host states at the same time

Redox-active metallodithiolene groups separated by insulating tetraphosphinobenzene spacers

Compounds of the type [(S2C2R2)M(μ-tpbz)M(S2C2R2)] (R = CN, Me, Ph, p-anisyl; M = Ni, Pd, Pt; tpbz = 1,2,4,5-tetrakis(diphenylphosphino)benzene) have been prepared by transmetalation with [(S2C2R2)SnR′2] reagents, by direct displacement of dithiolene ligand from [M(S2C2R2)2] with 0.5 equiv of tpbz, or by salt metathesis using Na2[S2C2(CN)2] in conjunction with X2M(μ-tpbz)MX2 (X = halide). X-ray crystallography reveals a range of topologies (undulating, chair, bowed) for the (S2C2)M(P2C6P2)M(S2C2) core. The [(S2C2R2)M(μ-tpbz)M(S2C2R2)] (R = Me, Ph, p-anisyl) compounds support reversible or quasireversible oxidations corresponding to concurrent oxidation of the dithiolene terminal ligands from ene-1,2-dithiolates to radical monoanions, forming [(−S•SC2R2)M(μ-tpbz)M(−S•SC2R2)]2+. The R = Ph and p-anisyl compounds support a second, reversible oxidation of the dithiolene ligands to their α-dithione form. In contrast, [(S2C2(CN)2)Ni(tpbz)Ni(S2C2(CN)2)] sustains only reversible, metal-centered reductions. Spectroscopic examination of [(−S•SC2(p-anisyl)2)Ni(μ-tpbz)Ni(−S•SC2(p-anisyl)2)]2+ by EPR reveals a near degenerate singlet–triplet ground state, with spectral simulation revealing a remarkably small dipolar coupling constant of 18 × 10–4 cm–1 that is representative of an interspin distance of 11.3 Å. This weak interaction is mediated by the rigid tpbz ligand, whose capacity to electronically insulate is an essential quality in the development of molecular-based spintronic devices

Open-ended metallodithiolene complexes with the 1,2,4,5-tetrakis(diphenylphosphino)benzene ligand: modular building elements for the synthesis of multimetal complexes

Open-ended, singly metalated dithiolene complexes with 1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz) are prepared either by ligand transfer to [Cl2M(tpbz)] from (R2C2S2)SnR′2 (R = CN, R′ = Me; R = Me, R′ = nBu) or by a direct reaction between tpbz and [M(S2C2R2)2] (M = Ni, Pd, Pt; R = Ph, p-anisyl) in a 1:1 ratio. The formation of dimetallic [(R2C2S2)M(tpbz)M(S2C2R2)] attends these syntheses in modest amounts, but the open-ended compounds are readily separated by silica chromatography. As affirmed by X-ray crystallographic characterization of numerous members of the set, the [(R2C2S2)M(tpbz)] compounds show dithiolene ligands in their fully reduced ene-1,2-dithiolate form conjoined with divalent Group 10 ions. Minor amounts of octahedral [(Ph2C2S2)2PtIV(tpbz)], a presumed intermediate, are isolated from the preparation of [(Ph2C2S2)PtII(tpbz)]. Heterodimetallic [(Ph2C2S2)Pt(tpbz)Ni(S2C2Me2)] is prepared from [(Ph2C2S2)PtII(tpbz)]; its cyclic voltammogram, upon anodic scanning, shows two pairs of closely spaced, but resolved, 1e– oxidations corresponding first to [R2C2S22–] – 1e– → [R2C2S•S–] and then to [R2C2S•S–] – 1e– → [R2(C═S)2]. The open diphosphine of [(R2C2S2)M(tpbz)] can be oxidized to afford open-ended [(R2C2S2)M(tpbzE2)] (E = O, S). Synthesis of the octahedral [(dppbO2)3Ni][I3]2 [dppbO2 = 1,2-bis(diphenylphosphoryl)benzene] suggests that the steric profile of [(R2C2S2)M(tpbzE2)] is moderated enough that three could be accommodated as ligands around a metal ion

Cationic Iridium Complexes Containing Anionic Iridium Counterions Supported by Redox-Active N-Heterocyclic Carbenes

The first cationic iridium complex supported by two bulky, ferrocenylated N-heterocyclic carbenes, [(1)(2)Ir-(COD)(+)[Cl](-) ([2]Cl+](-); 1 = 1-ferrocenylmethyl-3-mesityl-imidazol-2-ylidene, Fc-NHC; COD = cis,cis-1,5-cyclooctadiene), was synthesized and characterized. Treatment of the aforementioned complex with a mixture of [N(nBu)(4)](+)[Cl](-) and [Ir(COD)(Cl)](2) afforded [(I)(2)Ir(COD)(+)[Ir(COD)-(Cl)(2)](-) ([2](+)[Ir(COD)Cl-2](-)), which featured cationic as well as anionic Ir centers. Electrochemical analysis of [2](+)[Ir(COD)Cl-2](-) revealed that the complex displayed two reversible (iron- and iridium-centered) and two irreversible (iridium-centered) redox processes, which were assigned to the cationic and anionic components, respectively. Stirring [2](+)[Ir(COD)Cl-2](-) under an atmosphere of carbon monoxide generated the corresponding Ir carbonyl complex [(1)(2)Ir(CO)(2)](+)[Ir(CO)(2)(Cl)(2)](-) ([3](+)[Ir(CO)(2)Cl-2](-)). Cyclic voltammetry (CV) measurements of the aforementioned complexes containing [(1)(2)Ir(COD)](+) showed that the iron-centered oxidations were concurrent, reflective of limited electronic coupling between the two ferrocenyl moieties. However, spectroelectrochemical analysis of [(1)(2)Ir(CO)(2)](+)[BAr4F](-) revealed that the electron density at the Ir centers supported by the Fc-NHC ligands decreased upon oxidation of the ferrocenyl groups, as evidenced by a ca. 10 cm(-1) increase in the recorded v(CO) bands

Discovery of potential cyclooxygenase inhibitors using in silico docking studies

This study deals with the evaluation of the cyclooxygenase inhibitory activity of flavonoids (tangeritin, morin, rhamnetin, theaflavin, pachypodol, eriodictyol, homoeriodictyol, aromadedrin, okanin) using in silico docking studies. In silico docking studies were carried out using AutoDock 4.2. Three important parameters like binding energy, inhibition constant and intermolecular energy were determined. The results showed that all the selected flavonoids showed binding energy ranging between -8.77 kcalmol-1 to -6.10 kcalmol-1 when compared with that of the standard (-8.30 kcalmol-1). Intermolecular energy (-10.56 kcalmol-1 to -7.89 kcalmol-1) and inhibition constant (373.91 nM to 34.03 µM) of the ligands also coincide with the binding energy. All the selected flavonoids contributed cyclooxygenase inhibitory activity because of its structural parameters. These molecular docking analyses could lead to the further development of potent cyclooxygenase inhibitors.  

Metal-centered oxidations facilitate the removal of ruthenium-based olefin metathesis catalysts

Commercially available catalysts (SIMes)(PCy3)Cl2Ru(=CHPh) (2) and (SIMes)Cl2Ru(=CH-o-O-i-PrC6H4) (3) (SIMes = 1,3-dimesitylimidazolin-2-ylidene) were found to display reversible Ru oxidations via a series of electrochemical measurements. The redox processes enabled the catalysts to be switched between two different states of activity in ring opening metathesis polymerizations and ring closing metathesis reactions, primarily through changes in catalyst solubility. Moreover, treating a solution of 2 dissolved in C6H6/CH2Cl2/[1-butyl-3-methylimidazolium][PF6] (6:1:1.1 v/v/v) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was found to remove >99.9% of the catalyst, as determined by UV/vis spectroscopy. The methodology described herein establishes a new approach for controlling the activities displayed by commercially available olefin metathesis catalysts and for removing residual Ru species using redox-driven processes

Long-range spin coupling: a tetraphosphine-bridged palladium dimer

Two palladium monodithiolene units are linked by an insulating tetraphosphinobenzene ligand. This neutral compound can be reversibly two-electron oxidized to a dicationic compound formulated as [(adt·)PdII(μ-tpbz)PdII(adt·)]2+. The degenerate ground state leads to a spin-triplet EPR spectrum that is defined by an amazingly small zero-field splitting derived from weak dipolar coupling between the remote dithiolene radicals bridged by the insulating tetraphosphine unit