Complexes of Li, Na and Mg with 2D Allotropies of Second and Third Period. A Theoretical Study

Complexes of Li, Na and Mg with graphene, silicene, phosphorene nanoflakes (NFs) and their 2D allotropies have been studied at dispersion corrected TPSS/def-TZVP level of theory. The energy partition analysis of the complexes revealed that for most of the complexes exchange and correlation energies represent dominant contributions to the binding with strong charge transfer from metal atom to a NF. The exceptions are Mg complexes of graphene and phosphorene NFs where binding is due to dispersion and correlation terms. This difference is also reflected in large Mg-NF distances suggesting weak intermolecular interactions in these complexes. The calculated activation energies for metal hopping are easily achievable at room temperatures for carbon and silicon allotropies. However, they are significantly higher for phosphorus allotropies reaching almost 18 kcal/mol. There is a reasonably good correlation between the activation energies for hopping and binding energies for graphene, silicene and phosphorene NFs. Such correlation is not observed however for graphene, silicene and phosphorene 2D allotropies

Syntheses, structures and catalytic activity of tetranuclear Mg complexes in the ROP of cyclic esters under industrially relevant conditions

Tetranuclear magnesium imino(phenolate) complexes Mg4(L1–4)4 are excellent catalysts for the ROP of bulk rac-lactide and ε-caprolactone under industrially relevant conditions.

Let’s Uncomplicate: Mg Complexes in Mg3Sb2

A comment on "Understanding the Intrinsic <i>p</i>-type Behavior and Phase Stability of Thermoelectric a-Mg₃Sb₂" (Chong <i>et al.</i>, <i>ACS Applied Energy Materials</i>, <b>1</b>, 6600, 2018).

Let’s Uncomplicate: Mg Complexes in Mg3Sb2

A comment on "Understanding the Intrinsic <i>p</i>-type Behavior and Phase Stability of Thermoelectric a-Mg₃Sb₂" (Chong <i>et al.</i>, <i>ACS Applied Energy Materials</i>, <b>1</b>, 6600, 2018).

Bulky cationic β-diketiminate magnesium complexes

Cationic β-diketiminate Mg complexes with the bulky tBuBDI ligand and the weakly coordinating anion B(C6F5)4− have been prepared by the reaction of (tBuBDI)MgnBu with [Ph3C]+[B(C6F5)4]−; tBuBDI = CH[C(tBu)N-Dipp]2 and Dipp = 2,6-diisopropylphenyl.

Structural diversity of polynuclear Mg x O y cores in magnesium phenoxide complexes

The binuclear complex bis(2,6-di-tert-butyl-4-methylphenolato)-1κO,2κO-(1,2-dimethoxyethane-1κ2 O,O′)bis(μ-phenylmethanolato-1:2κ2 O:O)(tetrahydrofuran-2κO)dimagnesium(II), [Mg2(C7H7O)2(C15H23O)2(C4H8O)(C4H10O2)] or [(BHT)(DME)Mg(μ-OBn)2Mg(THF)(BHT)], (I), was obtained from the complex [(BHT)Mg(μ-OBn)(THF)]2 by substitution of one tetrahydrofuran (THF) molecule with 1,2-dimethoxyethane (DME) in toluene (BHT is O-2,6- t Bu2-4-MeC6H4 and Bn is benzyl). The trinuclear complex bis(2,6-di-tert-butyl-4-methylphenolato)-1κO,3κO-tetrakis(μ-2-methylphenolato)-1:2κ4 O:O;2:3κ4 O:O-bis(tetrahydrofuran)-1κO,3κO-trimagnesium(II), [Mg3(C7H7O)4(C15H23O)2(C4H8O)2] or [(BHT)2(μ-O-2-MeC6H4)4(THF)2Mg3], (II), was formed from a mixture of Bu2Mg, [(BHT)Mg( n Bu)(THF)2] and 2-methylphenol. An unusual tetranuclear complex, bis(μ3-2-aminoethanolato-κ4 O:O:O,N)tetrakis(μ2-2-aminoethanolato-κ3 O:O,N)bis(2,6-di-tert-butyl-4-methylphenolato-κO)tetramagnesium(II), [Mg4(C2H6NO)6(C15H23O)2] or Mg4(BHT)2(OCH2CH2NH2)6, (III), resulted from the reaction between (BHT)2Mg(THF)2 and 2-aminoethanol. A polymerization test demonstrated the ability of (III) to catalyse the ring-opening polymerization of ∊-caprolactone without activation by alcohol. In all three complexes (I)–(III), the BHT ligand demonstrates the terminal κO-coordination mode. Complexes (I), (II) and (III) have binuclear rhomboid Mg2O2, trinuclear chain-like Mg3O4 and bicubic Mg4O6 cores, respectively. A survey of the literature on known polynuclear Mg x O y core types for ArO–Mg complexes is also presented.

Cyclopentadienyl-based Mg complexes in the intramolecular hydroamination of aminoalkenes: mechanistic evidence for cationic versus neutral magnesium derivatives

Mechanistic evidence in the catalytic hydroamination of aminoalkenes for a cationic magnesium derivative.