Solvates of Manganese Trichloride Revisited – Synthesis, Isolation, and Crystal Structure of MnCl₃(THF)₃

Abstract

The syntheses and crystal structures of [MnCl3(H2O)(THF)2]·2THF (I), [MnCl4(THF)2][H(THF)2] (II), and [MnCl3(THF)3] (III) are reported. This study shows that former assumptions about the preparation of anhydrous MnCl3 and its etherates, published in the 1960s and earlier, have to be questioned. Instead of the conventional manganese sources, MnF3 was successfully utilized as starting material in THF to give water‐free MnCl3 etherates. These findings are vital for further reactions where reactive but anhydrous MnCl3 derivatives are needed.

Synthesis of a Bench-Stable Manganese(III) Chloride Compound: Coordination Chemistry and Alkene Dichlorination

“…The challenge with using “MnCl 3 ” is that solutions need to be prepared and used immediately and the speciation is often ill-defined precluding precise stoichiometry. Preparation of “MnCl 3 ” is commonly carried out by reduction of MnO 2 or permanganate with gaseous HCl at low temperature, and the compounds prepared this way must be manipulated and stored below −30 °C. ,− An alternative and more practical preparation of “MnCl 3 ” was developed by Christou and co-workers . Specifically, [Mn 12 O l2 (OAc) 16 (H 2 O) 4 ]·2HOAc·4H 2 O ( Mn 12 ) can be treated with Me 3 SiCl to afford deep purple solutions of nominally MeCN solvated MnCl 3 ( 2 ) .…”

Synthesis and Characterization of “Atlas-Sphere” Copper Nanoclusters: New Insights into the Reaction of Cu2+ with Thiols

“…While the H-bonded protons in these cations were not located in the difference Fourier map, their presence is supported by the close approach of two sets of THF molecules. Specifically, the distances between O3 and O4 (2.47(2) Å) and O8 and O8* (2.36(1) Å) are similar to the O–O distances in other [H­(THF) 2 ] + and [H­(Et 2 O) 2 ] + cations. − …”

“…Specifically, the distances between O3 and O4 (2.47(2) Å) and O8 and O8* (2.36(1) Å) are similar to the O-O distances in other [H(THF)2] + and [H(Et2O)2] + cations. [42][43][44][45][46][47][48][49] The 45 The presence of thiolate and thiol environments in a 6:4 ratio, instead of the expected 6:3 ratio, suggests that a small amount of excess of thiol is present in the final product, which we have been unable to remove.…”

Experimental and Computational Determination of a M–Cl Homolytic Bond Dissociation Free Energy: Mn(III)Cl-Mediated C–H Cleavage and Chlorination

“…The results from the coordination chemistry alone more than double the number of {Mn III Cl} complexes with facially coordinating tridentate ligands, 3,14 which is an important motif in the bioinorganic chemistry of Mn. 15,16 Some challenges in Mn(III) coordination chemistry are the intrinsic oxidative nature of Mn(III), 17,18 (1) 3 and solvated MnCl 3 ([MnCl 3 (MeCN) x ]) 19 to overcome the stated challenges. Furthermore, the tunable parameters, {M III Cl} substitution equilibria, and reduction potentials are control handles in strategic applications such as the emerging paradigm of C−H bond activations with M−halogens and M− pseudohalogens.…”

“…The results from the coordination chemistry alone more than double the number of {Mn III Cl} complexes with facially coordinating tridentate ligands, , which is an important motif in the bioinorganic chemistry of Mn. , Some challenges in Mn­(III) coordination chemistry are the intrinsic oxidative nature of Mn­(III), , lability of hexacoordinated {Mn III Cl} complexes, and the lack of suitable {Mn III Cl} synthons. In addition to the thermochemistry, this work continues our demonstration of the utility of bench-stable [MnCl 3 (OPPh 3 ) 2 ] ( 1 ) and solvated MnCl 3 ([MnCl 3 (MeCN) x ]) to overcome the stated challenges.…”