2019/10/17 by Werner Uhl, Frank Hengesbach, Jennifer Isermann +4
Chemistry · #Organoboron and organosilicon chemistry #Synthesis and characterization of novel inorganic/organometallic compounds #Organometallic Complex Synthesis and Catalysis
paper · pdf · doi:10.1002/zaac.201900195
Hydrogallation of Me 3 Si–C≡C–NR' 2 with R 2 Ga–H (R = t Bu, CH 2 t Bu, i Bu) yielded Ga/N‐based active Lewis pairs, R 2 Ga–C(SiMe 3 )=C(H)–NR' 2 ( 7 ). The Ga and N atoms adopt cis ‐positions at the C=C bonds and show weak Ga–N interactions. t Bu 2 GaH and Me 3 Si–C≡C–N(C 2 H 4 ) 2 NMe afforded under exposure of daylight the trifunctional digallium(II) compound [MeN(C 2 H 4 ) 2 N](H)C=C(SiMe 3 )Ga( t Bu)–Ga( t Bu)C(SiMe 3 )=C(H)[N(C 2 H 4 ) 2 NMe] ( 8 ), which results from elimination of isobutene and H 2 and Ga–Ga bond formation. 8 was selectively obtained from the ynamine and [ t Bu(H)Ga–Ga(H) t Bu] 2 [HGa t Bu 2 ] 2 . 7a (R = t Bu; NR' 2 = 2,6‐Me 2 NC 5 H 8 ) and H 8 C 4 N–C≡N afforded the adduct t Bu 2 Ga‐C(SiMe 3 )=C(H)(2,6‐Me 2 NC 5 H 8 ) · N≡C–NC 4 H 8 ( 11 ) with the nitrile bound to gallium. The analogous ALP with harder Al atoms yielded an adduct of the nitrile dimer or oligomers of the nitrile at room temperature. The reaction of 7a with Ph–N=C=O led to the insertion of two NCO groups into the Ga–C vinyl bond to yield a GaOCNCN heterocycle with Ga bound to O and N atoms ( 12 ).