Activation of non-polar bonds by an electron-rich gallagermylene.

The electron-rich germylene LGa(µ-Cl)GeArMes (1) (L = CH[C(Me)N(Dipp)]2, Dipp = 2,6-iPr2C6H3, ArMes = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) shows promising potential in the σ-bond activation of unpolar molecules as is shown in oxidative addition reactions with H2 and P4, yielding L(Cl)GaGe(H)2ArMes (2) and L(Cl)Ga(P4)GeArMes (3). Compounds 2 and 3 were characterised spectroscopically (1H, 13C{1H}, (31P{1H}), IR) and by single-crystal X-ray diffraction (sc-XRD).

Metal-coordinated distibene and dibismuthene dications - isoelectronic analogues of butadiene dications.

We report the synthesis and solid-state structures of DMAP-coordinated ([L(DMAP)GaPn]2[OTf]2; Pn = Sb 3, Bi 4) and base-free dipnictene dications ([LGaPn]2[BArFx]2, Pn = Sb: x = 24, 5a; 20, 5b; Bi: x = 24, 6a; 20, 6b). Quantum chemical calculations indicate that the dications 52+ and 62+ represent isoelectronic analogues of the butadiene dication.

Selective [2+1+1] Fragmentation of P4 by heteroleptic Metallasilylenes.

Small-molecule activation by low-valent main-group element compounds is of general interest. We here report the synthesis and characterization (1 H, 13 C, 29 Si NMR, IR, sc-XRD) of heteroleptic metallasilylenes L1 (Cl)MSiL2 (M=Al 1, Ga 2, L1 =HC[C(Me)NDipp]2 , Dipp=2,6-i Pr2 C6 H3 ; L2 =PhC(Nt Bu)2 ). Their electronic nature was analyzed by quantum chemical computations, while their promising potential in small-molecule activation was demonstrated in reactions with P4 , which occurred with unprecedented [2+1+1] fragmentation of the P4 tetrahedron and formation of L1 (Cl)MPSi(L2 )PPSi(L2 )PM(Cl)L1 (M=Al 3, Ga 4).

Bisstibane-distibane conversion via consecutive single-electron oxidation and reduction reaction.

peri-Substituted naphthalene complexes (Trip2Pn)2Naph (Pn = Sb 1, Bi 2) were synthesised and their redox behaviour investigated. Oxidation of 1 with [Fc][BArF] (BArF = B(C6F5)4) yielded [(Trip2Sb)(TripSb)Naph][BArF] (3) containing the stibane-coordinated stibenium cation [(Trip2Sb)(TripSb)Naph]+. Subsequent reduction of 3 with KC8 yielded distibane (TripSb)2Naph (4). 1-4 were characterised by NMR (1H, 13C) and IR spectroscopy as well as single-crystal X-ray diffraction (sc-XRD), while their electronic structures were analysed by quantum chemical computations.

Comparing London dispersion pnictogen-π interactions in naphthyl-substituted dipnictanes.

Using a combination of NMR, single crystal X-ray diffraction (sc-XRD) and quantum chemistry, the structure-directing role of London Dispersion (LD) is demonstrated for dibismuthane Bi2Naph2 (1). 1 shows intermolecular Bi⋯π contacts in the solid-state, while π⋯π interactions as observed in the lighter homologues are missing. Comparison of the whole series of dipnictanes revealed the influence of the pnictogen atom on the strength of London dispersion and highlights its importance in heavy main group element chemistry.