Spontaneous dehydrocoupling in peri-substituted phosphine-borane adducts.
نویسندگان
چکیده
Bis(borane) adducts Acenap(PiPr2·BH3)(PRH·BH3) (Acenap = acenaphthene-5,6-diyl; 4a, R = Ph; 4b, R = ferrocenyl, Fc; 4c, R = H) were synthesised by the reaction of excess H3B·SMe2 with either phosphino-phosphonium salts [Acenap(PiPr2)(PR)](+)Cl(-) (1a, R = Ph; 1b, R = Fc), or bis(phosphine) Acenap(PiPr2)(PH2) (3). Bis(borane) adducts 4a-c were found to undergo dihydrogen elimination at room temperature, this spontaneous catalyst-free phosphine-borane dehydrocoupling yields BH2 bridged species Acenap(PiPr2)(μ-BH2)(PR·BH3) (5a, R = Ph; 5b, R = Fc; 5c, R = H). Thermolysis of 5c results in loss of the terminal borane moiety to afford Acenap(PiPr2)(μ-BH2)(PH) (14). Single crystal X-ray structures of 3, 4b and 5a-c are reported.
منابع مشابه
Effect of the Phosphine Steric and Electronic Profile on the Rh-Promoted Dehydrocoupling of Phosphine–Boranes
The electronic and steric effects in the stoichiometric dehydrocoupling of secondary and primary phosphine-boranes H3B·PR2H [R = 3,5-(CF3)2C6H3; p-(CF3)C6H4; p-(OMe)C6H4; adamantyl, Ad] and H3B·PCyH2 to form the metal-bound linear diboraphosphines H3B·PR2BH2·PR2H and H3B·PRHBH2·PRH2, respectively, are reported. Reaction of [Rh(L)(η(6)-FC6H5)][BAr(F)4] [L = Ph2P(CH2)3PPh2, Ar(F) = 3,5-(CF3)2C6H3...
متن کاملHomogeneous, titanocene-catalyzed dehydrocoupling of amine-borane adducts.
Transition metal catalysis represents a relatively unexplored but potentially useful route to form bonds between main group elements. Previous work in the area of amine-borane adduct dehydrocoupling has exclusively employed late transition metal (e.g., Rh) catalysts which were found to predominantly operate via a heterogeneous mechanism. Herein, we present a new, early transition-metal-catalyze...
متن کاملIron Catalyzed Dehydrocoupling of Amine‐ and Phosphine‐Boranes
Catalytic dehydrocoupling methodologies, whereby dihydrogen is released from a substrate (or intermolecularly from two substrates) is a mild and efficient method to construct main group element-main group element bonds, the products of which can be used in advanced materials, and also for the development of hydrogen storage materials. With growing interest in the potential of compounds such as ...
متن کاملDehydrogenation of amine-boranes with a frustrated Lewis pair.
Bulky tertiary phosphine/borane Lewis pairs P(t)Bu(3)/B(C(6)F(5))(3) react with amine-boranes to afford dehydrocoupling products and phosphonium borohydride salts.
متن کاملA Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf-Stable Carbene Borane Complexes
N-Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6 F5 )3 depending on the orientation of the p...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
- Dalton transactions
دوره 45 5 شماره
صفحات -
تاریخ انتشار 2016