Increasing steric demand through flexible bulk – primary phosphanes with 2,6-bis(benzhydryl)phenyl backbones

Abstract

Novel primary phosphanes with bulky 2,6-bis(benzhydryl)phenyl substituents could be prepared and fully characterized.

Diaryltin Dihydrides and Aryltin Trihydrides with Intriguing Stability

“…iPr Ar*NH 2 and Me Ar*NH 2 ( iPr Ar* = 2,6-(Ph 2 CH) 2 -4-iPr-C 6 H 2 ; Me Ar* = 2,6-(Ph 2 CH) 2 -4-Me-C 6 H 2 ) were synthesized following procedures described in the literature [47]. Corresponding Ar*I compounds were isolated from diazotization of the aniline Ar*NH 2 [22]. Elemental analysis was performed with an Elementar Vario MICRO cube.…”

“…Due to their sterically demanding carbon backbone, anilines Ar*NH 2 (Ar* = 2,6-(Ph 2 CH) 2 -4-R-C 6 H 2 , R = e.g., Me, iPr) have been applied as sterically shielding amide ligands for low oxidation state group 14 compounds [23][24][25]. Just recently, corresponding Ar*I was isolated and applied in the synthesis of sterically encumbered primary phosphanes [22]. Nevertheless, activation of the rather acidic C-H bond in the CHPh 2 moiety is likely to happen [26].…”

“…Isolated diaryltin dihydrides 11 and 12 can be handled for a short period in air and possess an extraordinary thermal stability with melting points up to 200 • C. Likewise, isolated trihydrides 13 and 14 featuring this sterically crowded ligand Ar* possess astonishingly increased decomposition temperatures of up to 100 • C, while the parent PhSnH 3 slowly decomposes even at low temperatures [21]. 22 and −496.98, respectively; found in crude products of Ar*SnI 3 ) demonstrate a much stronger dependence on the nature of halide substituents, which is in full agreement with literature [32]. Even higher shifted resonances are observed for aryltin triiodides 9 and 10 (−937.27 and −939.57 ppm, respectively).…”

“…iPr Ar*I was isolated from diazotization of the aniline iPr Ar*NH 2 . [22] The crude product was recrystallized from acetone to give the product as a colorless solid.…”

“…Herein, we report the synthesis of diaryltin dihalides and aryltin trihalides and corresponding hydrides featuring a recently introduced bulky ligand backbone Ar* ( iPr Ar* = 2,6-(Ph 2 CH) 2 -4-iPrC 6 H 2 ; Me Ar* = 2,6-(Ph 2 CH) 2 -4-MeC 6 H 2 ) starting from the corresponding arly iodine Ar*I [22]. From the direct salt metathesis of in-situ prepared aryllithium solutions and SnCl 4 , we were able to isolate solely the diaryltin dichloride Ar* 2 SnCl 2 after recrystallization in good yields.…”