The reaction of 1,3,5-trimethyl-1,3,5-triazacyclohexane (TMTAC) with [La{Al(CH(3))(4)}(3)] resulted in C-H activation, leading to the formation of [(TMTAC)La{Al(CH(3))(4)}{(mu(3)-CH(2))[Al(CH(3))(2)(mu(2)-CH(3))](2)}] (1) containing a bis(aluminate) dianion and subsequent extrusion of methane. A similar reaction with [Y{Al(CH(3))(4)}(3)] led to the formation of CH(4), [TMTAC{Al(CH(3))(3)}(2)] (2) and {[(TMTAC)Y][Y(2)(mu(2)-CH(3))][{(mu(6)-C)[Al(mu(2)-CH(3))(2)(CH(3))](3)}{(mu(3)-CH(2))(mu(2)-CH(3))Al(CH(3))(2)}(2)] (3), containing a six-coordinate carbide ion and two [CH(2)Al(CH(3))(3)](2)(-) anions. Compound 3 is a product of multiple C-H activation. This reaction was monitored by in situ(1)H NMR spectroscopy. The analogous reaction with [Sm{Al(CH(3))(4)}(3)] led to the formation of 2, of [(TMTAC)Sm{(mu(2)-CH(3))(CH(3))(2)Al}(2){(mu(3)-CH(2))(2)Al(CH(3))(2)}(2)] (4), which contains a tris(aluminate) trianion, and [{(TMTAC)Sm}{Sm(2)(mu(2)-CH(3))}{(mu(6)-C)[Al(mu(2)-CH(3))(2)(CH(3))](3)}{(mu(3)-CH(2))(mu(2)-CH(3))Al(CH(3))(2)}(2)] (5), which is isostructural to 3. The products were characterised by elemental analyses (except 4, 5), 1 by multinuclear NMR spectroscopy and compounds 1, 2, 3, 4 and 5 by X-ray crystallography. Quantumchemical calculations were undertaken to support the crystallographic data analysis and confirm the structure of 3 and to compare it with an analogous compound where the central six-coordinate carbon has been replaced by oxygen. The investigations point to a mechanism of sterically induced condensation of [Al(CH(3))(4)](-) groups in close proximity in the coordination spheres of the rare-earth metal atoms, which is dependent on the size of these metal atoms.

Multiply iodinated biaryls can be prepared in yields up to 75% by direct oxidative coupling reaction of the iodinated arenes. The PIFA-mediated dehydrodimerization is superior to all other known methods. The developed protocol is reliable and easy to perform.

The reaction of the donor-functionalised N,N-bis(2-{pyrid-2-yl}ethyl)hydroxylamine and [LnCp3] (Cp=cyclopentadiene) resulted in the formation of bis(cyclopentadienyl) hydroxylaminato rare-earth metal complexes of the general constitution [Ln(C5H5)2{ON(C2H4-o-Py)2}] (Py=pyridyl) with Ln=Lu (1), Y (2), Ho (3), Sm (4), Nd (5), Pr (6), La (7). These compounds were characterised by elemental analysis, mass spectrometry, NMR spectroscopy (for compounds 1, 2, 4 and 7) and single-crystal X-ray diffraction experiments. The complexes exhibit three different aggregation modes and binding motifs in the solid state. The late rare-earth metal atoms (Lu, Y, Ho and Sm) form monomeric complexes of the formula [Ln(C5H5)2{eta2-ON(C2H4-eta1-o-Py)(C2H4-o-Py)}] (1-4, respectively), in which one of the pyridyl nitrogen donor atoms is bonded to the metal atom in addition to the side-on coordinating hydroxylaminato unit. The larger Nd3+ and Pr3+ ions in 5 and 6 make the hydroxylaminato unit capable of dimerising through the oxygen atoms. This leads to the dimeric complexes [(Ln(C5H5)2{mu-eta1:eta2-ON(C2H4-o-Py)2})2] without metal-pyridine bonds. Compound 7 exhibits a dimeric coordination mode similar to the complexes 5 and 6, but, in addition, two pyridyl functions coordinate to the lanthanum atoms leading to the [(La(C5H5)2{ON(C2H4-o-Py)}{mu-eta1:eta2-ON(C2H4-eta1-o-Py)})2] complex. The aggregation trend is directly related to the size of the metal ions. The complexes with coordinative pyridine-metal bonds show highly dynamic behaviour in solution. The two pyridine nitrogen atoms rapidly change their coordination to the metal atom at ambient temperature. Variable-temperature (VT) NMR experiments showed that this dynamic exchange can be frozen on the NMR timescale.

The first homoleptic anions of hydroxylaminato ate-complexes of yttrium and samarium of the formulae K[M(ON(i)Pr(2))(4)] (M = Y, Sm) have been prepared and structurally characterised featuring variations of the hapticity of their ON(i)Pr(2) ligands leading to different chain connectivities in their solid state aggregates.

The aminoalcohols MeNH(CH(2))(2)OH (), (t)BuNH(CH(2))(2)OH (), MeNH(CH(2))(3)OH (), (t)BuNH(CH(2))(3)OH () and MeNHCH(2)CMe(2)CH(2)OAlMe(2) () have been reacted with AlMe(3) to give the five corresponding aminoalkoxides of the general formula RNH-X-AlMe(2)- (X = organic spacer between N and O). (t)BuNHCH(2)CMe(2)CH(2)OH () reacts with AlMe(3) to give [(t)BuNHCH(2)CMe(2)CH(2)OAlMe(2)].AlMe(3) (.AlMe(3)). Analogous reactions of the aminoalcohols , , and with Al(t)Bu(3), GaMe(3) and Ga(t)Bu(3) afforded the corresponding aminoalkoxides of the general formula RNH-X-MR'(2)- (MR'(2) = Al(t)Bu(2)), - (MR'(2) = GaMe(2)) and - (MR'(2) = Ga(t)Bu(2)). The compounds were characterised by NMR spectroscopy, elemental analyses and mass spectrometry. Crystal structures were determined for , , .AlMe(3), , , and . Compounds and dimerise via Al(2)O(2) rings, while the amino-functions form intramolecular Al-N bonds. Compounds and form monomers with intramolecular Ga-N bonds. Compounds and are dimers via Ga(2)O(2) rings but in contrast to and without formation of intramolecular Ga-N bonds. .AlMe(3) also forms a monomeric compound with intramolecular AlN bond and a further AlMe(3) unit bonded to the O atom. The dynamic behaviour of and was investigated by variable-temperature NMR spectroscopy. Some compounds have different aggregation in solid and fluid phases.