114403-45-1

Upstream product

• 83095-83-4 [platinum(II)dichloride(1,2-bis(diphenylphosphino)ethane)] 
• 2923-28-6 silver trifluoromethanesulfonate 
• 1493-13-6 trifluorormethanesulfonic acid 
• 1663-45-2 1,2-bis-(diphenylphosphino)ethane 

Relevant academic research and scientific papers

Triphenylene based metal-pyridine cages

C3-symmetric pyridine containing tris-benzyl-O-substituted hexahydroxytriphenylene derivatives were prepared and used in combination with square-planar Pd(II) and Pt(II) complexes for the self-assembly of molecular cages in solution. The formation of a trigonal bipyramid M3L2 cage was demonstrated by multinuclear NMR analyses and pseudo 2D DOSY experiments and supported by semi-empirical calculations.

Regioselective double cycloplatination of 9,10-bis(diphenylphosphino) anthracene

Double eyclometalation of 9,10-bis(diphenylphosphino)anthracene (PAnP) by Pt(L)(OTf)2 (L = diphosphines, OTf = CF3SO3) gives rise to the geometrical isomers syn- and anti-[Pt2(L) 2(PAnP-H2)

NMR structure of an unusual Pt2(μ-BINOL) dimer: More surprises from a seemingly simple chiral ligand

A novel [(dppe)2Pt2(μ-BINOL)]2+[OTf]2 - dimer (A) was cleanly produced by addition of 1 equiv of HOTf to (dppe)Pt(S-BINOL) (1) or via comproportionation of 1 with (dppe)Pt-(OTf)2 (2). The structure of A was investigated by 1H, 31P, and 13C NMR spectroscopy, as well as 2D 1H/1H (COSY) and 13C/1H (HMQC, HMBC) correlation experiments, revealing that both halves of the bridging BINOL ligand have undergone enol-keto tautomerization in this complex. Two symmetry-equivalent (dppe)Pt fragments coordinate in an anti fashion via Pt-C σ bonds to the adjacent atoms C1 and C1′ of the resulting diketo BINOL ligand. η1-Coordination of the carbonyl groups of diketo BINOL to Pt was proposed to fill the fourth coordination site of each Pt square plane in dimer A, generating favorable five-membered Pt-chelate rings; the P-Pt coupling constants observed for A are consistent with C=0→Pt coordination. The driving force for dimer formation is likely electrostatic, as dimerization distributes the dicationic charge of Pt Lewis acid 2 over two Pt centers, facilitated by the diketo BINOL bridge.

Thermodynamic and kinetic relationships between Lewis acid-Lewis base complexes relevant to the P2Pt(OTf)2-catalyzed Diels-Alder reaction

The Pt(II) Lewis acids P2Pt(OTf)2 (2; P2 = dppe (a), R-BINAP (b)), which catalyze the Diels-Alder reaction of acryloyl-N-oxazolidinone (4) with cyclopentadiene (HCp), were generated in situ by activation of P2Pt(S-BINOL) precursors 1 with 2 equiv of triflic acid (HOTf). Catalysts 2 and catalytically relevant Lewis acid - Lewis base complexes [P2Pt(L2)]2+-[OTf]2- (L2 = 2 H2O (3), dienophile 4 (6), Diels-Alder adduct 5 (8)) were characterized by 1H and 31P NMR spectroscopy at 195 K. 2a was also characterized by X-ray crystallography. The thermodynamic relationships between 2, 3, 6, 8, and a BE4- analogue of 2 were determined through competitive binding experiments monitored by 31P NMR at 195 K, to assess the effects of competitive inhibition of counterions, additives, and product on substrate coordination to the catalyst. These experiments demonstrated that the Lewis bases bind to [P2Pt]2+ with relative strengths BF4- ? OTf- 2O. The rates of two ligand exchange processes (dienophile/dienophile (k1) and dienophile/OTf- (k2)) were measured at 270 K by simulation of exchange-broadened 31P NMR spectra of 2/6 equilibrium mixtures, revealing that ligand substitution occurs more rapidly in the dppe system than the R-BINAP system (180 times faster for k2). Finally, the reaction of HCp with 6 to give 8 was monitored by 31P and 1H NMR at 195 K; attack of HCp on Pt-coordinated 4 occurred much faster than ligand exchange, indicating that ligand exchange is the turnover-limiting step of the catalytic cycle.

Self-assembly and anion encapsulation properties of cavitand-based coordination cages

Two novel classes of cavitand-based coordination cages 7a-j and 8a-d have been synthesized via self-assembly procedures. The main factors controlling cage self-assembly (CSA) have been identified in (i) a P-M-P angle close to 90° between the chelating ligand and the metal precursor, (ii) Pd and Pt as metal centers, (iii) a weakly coordinated counterion, and (iv) preorganization of the tetradentate cavitand ligand. Calorimetric measurements and dynamic 1H and 19F NMR experiments indicated that CSA is entropy driven. The temperature range of the equilibrium cage-oligomers is determined by the level of preorganization of the cavitand component. The crystal structure of cage 7d revealed the presence of a single triflate anion encapsulated. Guest competition experiments revealed that the encapsulation preference of cages 7b,d follows the order BF4- > CF3SO3- ? PF6- at 300 K. ES-MS experiments coupled to molecular modeling provided a rationale for the observed encapsulation selectivities. The basic selectivity pattern, which follows the solvation enthalpy of the guests, is altered by size and shape of the cavity, allowing the entrance of an ancillary solvent molecule only in the case of BF4-.

Trifluoromethanesulphonato-O Complexes of Platinum(II) and Palladium(II)

Reaction of chloroplatinum(II) and chloropalladium(II) complexes containing amine, pyridine (py), or phosphine ligands at or above room temperature with anhydrous CF3SO3H leads to formation of trifluoromethanesulphonato-O complexes, characterized spectros