Recent Advances in Phosphinoborane Chemistry

A Bicyclic P–P‐Bridged 1,3,2,4‐Diphosphadiboretane Cation and an Imino(phosphinidene)borane–AlBr3 Adduct

“…The state of the art has been summarized in a review. [2] Particularly 1,3,2,4-diphosphadiboretanes [3][4][5][6][7][8][9][10][11] offer many interesting aspects as ligands as well as a source for amino-phosphinidene-boranes R 2 N=B=PR [8,11] having a boron atom of coordination number 2 and B=N as well as B=P double bonds. They also react with many Lewis acids often in rather unusual ways, [12] and we report here on the reaction of [tmpB-PtBu] 2 , 1, (tmp = 2,2,6,6-tetramethylpiperidino) with AlBr 3 .…”

Main Group Lewis Acid/Base‐Stabilised Phosphanylboranes

“…The parent compound H 2 P-BH 2 can be stabilised with NMe 3 as the Lewis base and B(C 6 F 5 ) 3 (1) or Ga(C 6 F 5 ) 3 (2) as the main group Lewis acid. Furthermore the synthesis of the phenyl-substituted LA/LB stabilised phosphanylboranes 4 and 5 was achieved.…”

“…[1] However, attempts to isolate the parent compound of this class (H 2 P-BH 2 ) (A) (Scheme 1) have been futile, and only theoretical investigations on A have been performed. [2] Oligophosphanylboranes with the general formula (HRP-BH 2 ) n can be synthesised via dehydrocoupling reactions at elevated temperatures [3] or catalysed by either Rh I complexes (R = Ph) [4] or B(C 6 F 5 ) 3 (R = H).…”

“…[5] Experimentally accessible monomeric phosphanylboranes are mostly stabilised by sterically demanding substituents to avoid intermolecular oligomerisation. [1] Our approach to the parent compounds of phosphanylboranes was to stabilise them by the coordination of Lewis acids and Lewis bases as type B compounds. By this way the lone pair of the pnicogen is occupied by a Lewis acid (LA) and the Group 13 element is coordinated by a Lewis base (LB) (B).…”

“…[6] In contrast, less is known about main group Lewis acid stabilised group 13/15 compounds. [5,7,8] ence on the reactivity of the phosphanylboranes [Equation (1)]. For example, photolysis of compound D leads to a dimer with elimination of CO and H 2 .…”