Palladium-catalyzed direct ortho-silylation of oxalyl amide-protected phenylmethanamine and phenethylamine with commercially available disilanes is reported. Germanylation products were also produced under the same reaction conditions. This protocol tolerated oxalyl amide-protected aliphatic amines, which gave γ-C-H silylation products.

The results from a direct palladium-catalyzed cross-coupling reaction between a variety of olefins with acrylate through vinylic C-H activation that give the corresponding butadienes in moderate to good yields and stereoselectivities are reported. Given the reaction's ability to tolerate a wide range of styrenes, aliphatic alkenes and acrylates, this atom-and step-economical methodology offers a straightforward method to forge new C-C bonds of the valuable diene products from readily available starting materials under very mild reaction conditions.

Reaction of CH(3,5-Me 2 Pz) 2 (CO) 3 WSnAr 3 (Pz ) pyrazol-1-yl; Ar ) phenyl or p-tolyl) with hydrogen halide results in the formation of one Sn-C sp3 bond with the cleavage of one Sn-C Ar bond as well as the W-C sp3 bond to give novel heterodinuclear complexes Ar 2 SnCH-(3,5-Me 2 Pz) 2 (CO) 3 WX (X ) Cl or Br), in which an intriguing κ 3 -[N,Sn,N] coordination mode as well as an unsymmetrically semibridging carbonyl between the W-Sn bond is observed.

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Diphenyl(vinyl)stannylbis(3,5-dimethylpyrazol-1-yl)methane and diphenyl(vinyl)stannylbis(3,4,5-trimethylpyrazol-1-yl)methane have been synthesized by the reaction of bis(3,5-dimethylpyrazol-1-yl)methyl or bis(3,4,5trimethylpyrazol-1-yl)methyllithium with diphenyl(vinyl)tin iodide. Treatment of these bis(pyrazol-1-yl)methanes modified by the vinyltin groups with M(CO) 5 THF (M＝Mo and W) in refluxing THF resulted in new heterobimetallic complexes R 3 SnCHPz 2 M(CO) 3 (R 3 Sn represents trivinyltin or diphenyl(vinyl)tin, and Pz represents substituted pyrazol-1-yl), in which a vinyl group bonds to the molybdenum or tungsten atom in η 2 -fashion to lead to bis(pyrazol-1-yl)methanes acting as a tridentate κ 3 -(π,N,N) ligand. Reaction of (CH 2 ＝ CH) 3 SnCH(3,5-Me 2 Pz) 2 W(CO) 3 and Ph 2 (CH 2 ＝CH)SnCH(3,5-Me 2 Pz) 2 W(CO) 3 with I 2 has been investigated. The former gave a complex CH 2 (3,5-Me 2 Pz) 2 W(CO) 4 , while the latter yielded a four-membered heterometallocyclic complex CH(3,5-Me 2 Pz) 2 W(CO) 3 I with the loss of the organotin group. Treatment of this four-membered heterometallocyclic complex with PhSNa led to the iodide anion replaced by the thiophenolate anion to give a complex CH(3,5-Me 2 Pz) 2 W(CO) 3 SPh.