Phosphanylhydrosilylalkynes R2HSiCCPAr2 (R,Ar: Me,4‐tBuC6H4 1, Me,Mes 2, Mes,Ph 3; Mes = 2,4,6‐Me3C6H2) were prepared and the reactions with B(C6F5)3 were studied. Reaction of 1 and B(C6F5)3 produced E‐alkene {(E)‐(C6F5)3BCHC[P(4‐tBuC6H4)2]SiMe2}2 (4) and that of 2 and B(C6F5)3 yielded Z‐alkene (Z)‐(C6F5)2BCHC(PMes2)SiMe2(C6F5) (5). The former is proposed to go through a key [Me2HSi]+ for function while the latter via the phosphacyclopropene intermediate, both of which are a result by self‐hydrosilylation. Reaction of 3 and B(C6F5)3 generated at room temperature a P→B coordination compound Mes2HSiCCP(Ph2)B(C6F5)3 (6) and at 100 °C the 1,1‐carboboration E‐alkene (E)‐Mes2HSi(Ph2P)CC(C6F5)B(C6F5)2 (7). Kinetic study and DFT calculations were accomplished for reaction of 2 and B(C6F5)3 to 5. The mechanisms of these reactions have been discussed. The reactions of the P/Si+ LPs Me2Si(Ph2P)CCHB(C6F5)3}2 (3a) and 4 were also investigated. Compound 4 disassociated H2O into {(E)‐(C6F5)3BCHC[PH‐4‐tBuC6H4)2]Si(Me2)}2(µ‐O) (8) and (E)‐(C6F5)3BCHC[PH(4‐tBu‐C6H4)2]Si(Me2)O(HNC5H5) (9). Compound 3a reacted with tBuNCO by [3+2] dipolar cycloaddition to give a C2OPSi‐heterocycle [(C6F5)3BHC]CSi(Me2)P(Ph2)OC(NtBu) (10). Furthermore, 4 reacted with tBuNCO and then H2O to afford (E)‐(F5C6)3BHCC[P(4‐tBuC6H4)2C(O)NHtBu][Si(Me2)OH(NC5H5)] (11) through a C2OPSi‐heterocycle intermediate followed by the H2O‐disassociation under the C2OPSi‐ring opening.

Phosphanylhydrosilylalkynes Me2HSiC[triple bond, length as m-dash]CPAr2 (Ar = Ph, 1a; 4-MeC6H4, 1b) were synthesized, which reacted with B(C6F5)3 to produce alkenes [(E)-(C6F5)3BCH[double bond, length as m-dash]C(PAr2)SiMe2]2 (2a and 2b) and (Z)-(C6F5)2BCH[double bond, length as m-dash]C(PAr2)SiMe2(C6F5) (3a and 3b). The formation of 2a (or 2b) involved a Wrackmeyer's SiHMe2 migration followed by Si-H addition across the C[triple bond, length as m-dash]C bond, whereas, that of 3a (or 3b) involved a similar mechanism with a further C6F5 migration. The B(C6F5)3-promoted reaction of the Si-centered geminal H and C[triple bond, length as m-dash]C groups is thus realized, which may be considered as a self-hydrosilylation. Mechanistic studies by both variable temperature NMR spectroscopy and DFT calculations were accomplished.

The 2-aminophenylaluminum dihydride (2-TMP-C6 H4 )AlH2  (2) has been prepared and characterized for the first time. Compound 2 features an intramolecular N⋅⋅⋅Al donor-acceptor bond. 2 reacted with N-methylpyrrole and N-methylindole (both at 50 °C) by means of the elusive AlH C(sp2 )-H dehydroalumination to aluminum heteroaryls (3 and 4). Moreover, 2 reacted with PhCCSiMe3 (at room temperature) and Ph2 CCNR (R=iPr or 2,6-iPr2 C6 H3 , at -30 to 20 °C ) to yield aluminaindene heterocycle (8) and alumina-aza-naphthalene heterocycle (9 and 10), respectively. These reactions underwent hydroalumination followed by AlH C(sp2 )-H dehydroalumination. The reaction mechanism has been studied by combining experiment and quantum chemical calculations, with the result that the key heteroarene or arene C(sp2 )-H bond activation is involved under cooperative interaction by the inherent N/Al donor/acceptor pair. The reported reactions open a straightforward route to heteroaryl and unique heterocyclic aluminum compounds.

Aryl(silyl)amino group stabilized hydridosilanediols RSiH(OH)2 (R = N(SiMe2Ph)-2,6-iPr2C6H3 (), N(SiMe3)-2,6-iPr2C6H3 (), and N(SiMe2Ph)-2,4,6-Me3C6H2 ()) were prepared from the controlled hydrolysis of the related RSiHCl2 () each in the presence of aniline as the HCl acceptor. Reactions of with AlMe3, AliBu3, AlH(iBu)2, and AlH3·NMe3, respectively, yielded alumino(hydrido)siloxanes [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlMe(THF)]2 (), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAliBu(THF)]2 (), [2,6-iPr2C6H3N(SiMe2Ph)Si(H)O2]3[Al(THF)]2 (), and [2,6-iPr2C6H3N(SiMe2Ph)Si(H)OAlH(THF)]2 (). The reaction of with AlMe3 gave [2,6-iPr2C6H3N(SiMe3)Si(H)OAlMe(THF)]2 (), a compound similar to . Compounds are characterized by NMR ((1)H, (13)C, and (29)Si) and IR spectroscopy and CHN elemental analysis, of which and are further studied by X-ray crystallography. Compounds and feature cyclic structures all with the skeleton core of Si2O4Al2 while compound exhibits a bicyclic structure having a core of Si3O6Al2. Melting point measurements indicated that are thermally stable bearing the geminal SiH and SiOH groups. Compounds and are thermally stable as well with the O atom-bridged SiH and AlR (R = Me, iBu, or H) groups.