Facile routes to manganese(II) triflate complexes

Abstract

Manganese(II) chloride reacts with trimethylsilyl triflate (TMS(OTf) where OTf = -OSO2CF3) in a 1:1 mixture of acetonitrile and tetrahydrofuran, and after recrystallization affords the linear coordination polymer [MnII(CH3CN)2(OTf)2]n. Each distorted octahedral manganese(II) center in the polymeric chain has trans-acetonitriles and the remaining equatorial coordination positions are occupied by the bridging triflate anions. Dissolving [MnII(CH3CN)2(OTf)2]n in equal volumes of acetonitrile and pyridine followed by recrystallization with diethyl ether yields trans-[MnII(C5H5N)4(OTf)2]. The distorted octahedral geometry of the manganese center features monodentate trans-triflate anions and four equatorial pyridines. Exposure of either [MnII(CH3CN)2(OTf)2]n or [MnII(C5H5N)4(OTf)2] to water readily gives [MnII(H2O)6](OTf)2. XRD reveals hydrogen-bonding interactions between the [MnII(H2O)6]2+ cation and the triflate anion. All three of these species are easily crystallized and provide convenient sources of manganese(II) for further synthetic elaboration.

Tuning Second Coordination Sphere Interactions in Polypyridyl–Iron Complexes to Achieve Selective Electrocatalytic Reduction of Carbon Dioxide to Carbon Monoxide

“…David Z. Zee, 1,6,8 Michael Nippe, 1,6,7,8 Amanda E. King, 1 Christopher J. Chang, 1,2,4 * and Jeffrey R. Long, 1,3,5,6 * Departments of 1 Chemistry, 2 Molecular and Cell Biology, 3 Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720, United States 4 Chemical Sciences Division, 5 Materials Sciences Division, and the 6 *E-mail: chrischang@berkeley.edu (C.J.C. ), jrlong@berkeley.edu (J.R.L.…”

“…Cost-effective solar-to-chemical conversion requires the identification of efficient electrocatalysts that are built solely from earth-abundant elements. [1][2][3] Powering the conversion of carbon dioxide (CO2) via solar-derived potential energy would allow for the regeneration of carbon-based fuels and the utilization of CO2 as an inexpensive C1 feedstock molecule for industrial applications. Various heterogeneous electrocatalytic CO2 reduction systems have been reported that utilize non-precious metal surfaces, [4][5][6][7][8][9][10][11][12] molecularly-inspired covalent 13 and metalorganic frameworks, [14][15][16] and surface-attached molecular catalysts.…”

Metal Trimethylsilylthiolates for the Synthesis of Trinuclear MnPd2 Complexes

“…When orange solutions of 3 were reacted with [Mn(CH 3 CN) 2 (OTf) 2 ] in THF at room temperature, a deep red solution formed. After filtration and layering the solution with a counter‐solvent and allowing slow mixing at –25 °C for 2 d, the complex [MnOTf(thf) 2 (μ 3 ‐S) 2 Pd 2 (dppp) 2 ]OTf 4 was obtained as deep red, fragile crystals in 45 % yield (Scheme ).…”

“…Celite ® was dried by heating at 120 °C under vacuum for 48 h. All other chemicals were used as received from Alfa Aesar and/or Sigma Aldrich without further purification. Starting reagents Li[SSiMe 3 ], [Li( N , N ′‐tmeda)] 2 [Mn(SSiMe 3 ) 4 ], [Mn(CH 3 CN) 2 (OTf) 2 ], [PdCl 2 (dppp)], and [Pd(OAc) 2 (dppp)] were synthesized using literature procedures.…”

Intramolecular C–H and C–F Bond Oxygenation by Site-Differentiated Tetranuclear Manganese Models of the OEC

“…All reagents were used as received unless otherwise stated. Sodium 5-phenylpyrazolate (NaPhPz), 20a sodium 5-(2,6-difluoro)phenylpyrazolate (NaF2ArPz), 20a sodium 2-(1 H -pyrazol-5-yl)phenolate (NaOArPzH), 20a sodium 3-fluoro-2-(1 H -pyrazol-5 yl)phenolate (NaOFArPzH), 20a iodosobenzene (PhIO), 38 silver tetraphenylborate (AgBPh 4 ), 39 and Mn(OTf) 2 (MeCN) 2 40 were prepared according to literature procedures. Caution!…”