Rivard Eric, Merrill W Alexander, Fettinger James C, Wolf Robert, Spikes Geoffrey H, Power Philip P
Department of Chemistry, University of California, Davis, California 95616, USA.
Inorg Chem. 2007 Apr 16;46(8):2971-8. doi: 10.1021/ic062076n. Epub 2007 Mar 6.
Reaction of the hindered phosphino- and arsinoboranes, ArPn(H)-B(Br)Tmp (Ar = -C6H3-2,6-(C6H2-2,4,6-iPr3)2; Tmp = 2,2,6,6-tetramethylpiperidino; Pn = P and As, 1 and 3, respectively) with 4-dimethylaminopyridine, DMAP, afforded the boranylidenephosphane and arsane, ArPn=B(DMAP)Tmp (Pn = P and As, 2 and 4) as deep red-purple solids. The analogous aminoboranes Ar'N(H)-B(X)Tmp (Ar' = -C6H3-2,6-(C6H2-2,4,6-Me3)2; X = Cl and Br; 5 and 6) did not display any reactivity with DMAP, but in the presence of the amide base, Na[N(SiMe3)2], the clean formation of the uncomplexed iminoborane Ar'NBTmp (7) was observed. Attempts to generate an Sb=B bond were unsuccessful, as the required stibinoborane precursor, ArSb(H)-B(Br)Tmp, could not be prepared; in place of clean Sb-B bond formation, the reduced product ArSb=SbAr was obtained. All compounds were characterized spectroscopically, and the X-ray crystal structures of 1, 2, 4, 6, and 7 were determined.
