Starting reagents were prepared as described in literature. [Al(DMP)Cl2] was synthesized following a route described by Mai et al. Literature known compounds, either for comparison or for first time thermal evaluation were synthesized according to the respective reported procedures: Compound 7 was synthesized as described by Blakeney et al. , and 4 -6 following the procedure reported by Ruff et al. NMR-spectra were recorded on Bruker Avance III 300 and referenced to the internal solvent signal (C6D6). Spectra analysis was done with the software MestReNova v10.0.2-15465 from Mestrelab Research S.L. Elemental analysis (EA) was performed on an Elementar Vario Micro Cube. Electron Impact Mass spectra (EI-MS) were recorded at the RubioSpec Service Center of the Ruhr-University Bochum with a Varian MAT spectrometer at an ionizing energy of 70 eV. IR spectra were recorded on a FTIR spectrometer Spectrum Two by PerkinElmer placed in an argon filled glove box, utilizing an UATR Two ATR-unit by PerkinElmer. Thermogravimetric analysis (TGA) was performed on a Netzsch STA 409 PC at ambient pressure (sample size ≈ 10 mg), with a heating rate of 5 K min -1 (N2 flow rate = 90 sccm), placed in an argon (Air Liquide, 99.995 %) filled glove box (SylaTech). In the DFT calculations, all structures were fully optimized with no symmetry constraints using the TURBOMOLE suite 44,45 of quantum chemistry programs. All calculations were performed with the PBE exchange-correla on func onal and a polarized triple ζ basis set (def-TZVPP) . The SCF convergence criterion was set to 10 -6 Ha and a medium (m3) grid was used for the integrations.