Bis[(trimethylsilyl)methyl]manganese: Structural Variations of Its Solvent-Free and TMEDA-, Pyridine-, and Dioxane-Complexed Forms
First synthesized in 1976 and recently taking on a new significance as a key precursor to heterobimetallic alkali-metal-manganese(II) complexes, bis[(trimethylsilyl)methyl] manganese has been structurally characterized by X-ray crystallography. It forms a polymeric chain structure of formula [{Mn(CH2SiMe3)(2)}(infinity)], 1, in which distorted tetrahedral, spiro Mn atoms are linked together via mu(2)-bonding alkyl ligands. The structure is notable for displaying two distinct categories of Mn-C bond lengths with a mean size differential of 0.225 angstrom and for being the first fully crystallographically characterized polymeric manganese(II) dialkyl compound. Magnetic measurements of 1 indic…
Tuning the Basicity of Synergic Bimetallic Reagents: Switching the Regioselectivity of the Direct Dimetalation of Toluene from 2,5‐ to 3,5‐Positions
Meta-meta metalation: Remarkably, toluene can be directly dimanganated or dimagnesiated at the 3,5-positions using bimetallic bases with active Me3SiCH2 ligands (see scheme, blue). In contrast, n-butyl ligands lead to 2,5-metalation (red). tmp=2,2,6,6-tetramethylpiperidide.
Structural and Magnetic Insights into the Trinuclear Ferrocenophane and Unexpected Hydrido Inverse Crown Products of Alkali‐Metal‐Mediated Manganation(II) of Ferrocene
With the aim of introducing the diisopropylamide [NiPr(2)](-) ligand to alkali-metal-mediated manganation (AMMMn) chemistry, the temperature-dependent reactions of a 1:1:3 mixture of butylsodium, bis(trimethylsilylmethyl)manganese(II), and diisopropylamine with ferrocene in hexane/toluene have been investigated. Performed at reflux temperature, the reaction affords the surprising, ferrocene-free, hydrido product [Na(2)Mn(2) (mu-H)(2){N(iPr)(2)}(4)]2 toluene (1), the first Mn hydrido inverse crown complex. Repeating the reaction rationally, excluding ferrocene, produces 1 in an isolated crystalline yield of 62 %. At lower temperatures, the same bimetallic amide mixture leads to the manganati…