Synthese, Struktur, Tautomerie und Reaktivität von Methantrisamidinen

Heterobimetallic Metal–Amidinate Complexes by Stepwise Metalation of Methanetrisamidines

“…of their corresponding metal alkyls MMe n +1 at 100 °C and prolonged reaction times yielded the homometallic tetranuclear complexes {C[C(NPh) 2 ] 3 [MMe n ] 4 } [MMe n = AlMe 2 ( 4a ), GaMe 2 ( 4b ), ZnMe ( 4c )] (Scheme ). Complex 4a , which was reported previously,8 was identified by NMR spectroscopy, whereas 4b and 4c were characterized by NMR and single‐crystal X‐ray diffraction. Because the quality of the crystals of 4c was poor, only the connectivity of the model could be established.…”

“…The C–C bond lengths in 3a [C1–C2 1.4564(19) Å, C1–C3 1.453(2) Å, C1–C4 1.446(2) Å] are very similar and their values are between those of typical C–C single and double bonds, which indicates complete delocalization of the π‐electron density within this C 4 moiety. In contrast, in the four‐fold metalated complex {C[C(NPh) 2 ] 3 [AlMe 2 ] 4 } ( 4a ), two short [1.4191(15) Å] and one elongated C–C bonds [1.506(2) Å] were observed 8. The Al–N bond lengths in 3a (av.…”

“…91.92°) and C–Al–C bond angles [118.58(9), 115.46(11)°] are comparable to those previously reported for the bridging AlMe 2 moieties in the tetrametalated Al complex {C[C(NPh) 2 ] 3 [AlMe 2 ] 4 } [ 4a ; av. Al–N 1.9587 Å, C–Al–C 119.60(6)°, N–Al–N 90.67(5)°] 8…”

“…Solvents were dried with Na/K and degassed prior to use. Compound 1c was prepared according to literature methods 8 . 1 H and 13 C NMR spectra were recorded with a Bruker DMX 300 spectrometer and are referenced to internal C 6 D 5 H ( 1 H: δ = 7.154 ppm; 13 C: δ = 128.0 ppm) and CD 2 Cl 2 ( 1 H: δ = 5.32 ppm; 13 C: δ = 53.8 ppm).…”

“…We recently reported the synthesis of two methanetrisamidines {HC[C(NR)NHR] 3 } [R = i Pr ( 1a ), Ph ( 1b )] and the tautomeric form{C[C(NPh)N(Ph)H] 2 [C(HNPh) 2 ]} ( 1c ; Scheme ),8 which were formed by hydrolysis of tetranuclear zinc amidinate complexes {C[C(NR) 2 ZnMe] 4 } [R = i Pr ( 2a ), Ph ( 2b )] 9. Moreover, the ability of these multifunctional molecules to stabilize homometallic complexes was shown through alkane elimination reactions with aluminium organyls.…”