Hungry for charge – how a beryllium scorpionate complex “eats” a weakly coordinating anion

We present the reaction of a tris(pyrazolyl) beryllium scorpionate (TpBe) complex with a weakly coordinating anion (WCA), which yields the heteroleptic complex TpBeOC(CF3)31 (TpBeORF). The product 1 has been characterized by multinuclear NMR spectroscopy (1H, 9Be, 13C) and single-crystal X-ray diffraction (scXRD). Quantum chemical calculations (DFT, NPA, LOL) were performed to study the bonding nature in 1.

Magnesium bis(amidinate) and bis(guanidinate) complexes: impact of the ligand backbone and bridging groups on the coordination behaviour

By dealing with various bis(amidine)s or bis(guanidine)s and different magnesium sources, we got a full house of homoleptic complexes. However, the joker card showing a heteroleptic complex is waiting to be used.

Synthesis, solid-state structures and reduction reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexes

A series of new heteroleptic divalent germaniun and tin complexes of the general type L1,4GeN(SiMe3)2 (1, 2) and L1−4SnN(SiMe3)2 (3–6) were synthesized by reaction of β-ketimines L1−4H with Ge[N(SiMe3)2]2 and Sn[N(SiMe3)2]2, respectively. The reaction of 3 with the strong Mg(I) reductant L5Mg yielded the heteroleptic complex L1MgL57 after ligand transfer from tin to magnesium, whereas analogous reactions of L4GeN(SiMe3)22 and L4SnN(SiMe3)26 with L5Mg occurred with formation of insoluble precipitates, transfer of the amido substituent from the group 14 metal to magnesium and subsequent formation of the heteroleptic magnesium complex L5MgN(SiMe3)2 (8). 1–8 were characterized by heteronuclear NMR (1H, 13C, 119Sn) and IR spectroscopy, elemental analysis and single-crystal X-ray diffraction (L4SnN(SiMe3)26, L1MgL57).

Solvent dependence of the solid-state structures of salicylaldiminate magnesium amide complexes

There are challenges in using magnesium coordination complexes as reagents owing to their tendency to adopt varying aggregation states in solution and thus impacting the reactivity of the complexes. Many magnesium complexes are prone to ligand redistributionviaSchlenk equilibrium due to the ionic character within the metal–ligand interactions. The role of the supporting ligand is often crucial for providing stability to the heteroleptic complex. Strategies to minimize ligand redistribution in alkaline earth metal complexes could include using a supporting ligand with tunable sterics and electronics to influence the degree of association to the metal atom. Magnesium bis(hexamethyldisilazide) was reacted with salicylaldimines [1L=N-(2,6-diisopropylphenyl)salicylaldimine and2L= 3,5-di-tert-butyl-N-(2,6-diisopropylphenyl)salicylaldimine] in either nondonor (toluene) or donor solvents [tetrahydrofuran (THF) or pyridine]. The structures of the magnesium complexes were studied in the solid stateviaX-ray diffraction. In the nondonor solvent,i.e.toluene, the heteroleptic complex bis{μ-2-[(2,6-diisopropylphenyl)iminomethyl]phenolato}-κ3N,O:O;κ3O:N,O-bis[(hexamethyldisilazido-κN)magnesium(II)], [Mg2(C19H22NO)2(C6H18NSi2)2] or [1LMgN(SiMe3)2]2, (1), was favored, while in the donor solvent,i.e.pyridine (pyr), the formation of the homoleptic complex {2,4-di-tert-butyl-6-[(2,6-diisopropylphenyl)iminomethyl]phenolato-κ2N,O}bis(pyridine-κN)magnesium(II) toluene monosolvate, [Mg(C27H38NO)2(C5H5N)2]·C5H5N or [{2L2Mg2(pyr)2}·pyr], (2), predominated. Heteroleptic complex (1) was crystallized from toluene, while homoleptic complexes (2) and the previously reported [1L2Mg·THF] [Quinqueet al.(2011).Eur. J. Inorg. Chem.pp. 3321–3326] were crystallized from pyridine and THF, respectively. These studies support solvent-dependent ligand redistribution in solution.In-situ1H NMR experiments were carried out to further probe the solution behavior of these systems.

Aluminium(III) amidinates formed from reactions of `AlCl' with lithium amidinates

The disproportionation of AlCl(THF)n(THF is tetrahydrofuran) in the presence of lithium amidinate species gives aluminium(III) amidinate complexes with partial or full chloride substitution. Three aluminium amidinate complexes formed during the reaction between aluminium monochloride and lithium amidinates are presented. The homoleptic complex tris(N,N′-diisopropylbenzimidamido)aluminium(III), [Al(C13H19N2)3] or Al{PhC[N(i-Pr)]2}3, (I), crystallizes from the same solution as the heteroleptic complex chloridobis(N,N′-diisopropylbenzimidamido)aluminium(III), [Al(C13H19N2)2Cl] or Al{PhC[N(i-Pr)]2}2Cl, (II). Both have two crystallographically independent molecules per asymmetric unit (Z′ = 2) and (I) shows disorder in four of its N(i-Pr) groups. Changing the ligand substituent to the bulkier cyclohexyl allows the isolation of the partial THF solvate chloridobis(N,N′-dicyclohexylbenzimidamido)aluminium(III) tetrahydrofuran 0.675-solvate, [Al(C19H27N2)2Cl]·0.675C4H8O or Al[PhC(NCy)2]2Cl·0.675THF, (III). Despite having a twofold rotation axis running through its Al and Cl atoms, (III) has a similar molecular structure to that of (II).