“…Compared to previous methods shown in Scheme 1, our methods presented here are expected to provide facile, convenient, and selective routes to various Pd(II) or Pt(II) tetrazolethiolates. We further examined small-molecule insertion reactions using an organic isocyanide as well as reactions involving electrophiles, which led to the isolation of new Pd(II) tetrazoletetrazole-thiolato complexes such as trans-[PdS{CN 4 (R)} 2 (PR 3 ) 2 ] (R = Ph, Me, allyl, i-Pr, indanyl; PMe 3 , PEt 3 ) 26a,f Pd-S = 2.33-2.40 Å, trans-[PdS{CN 4 (R)} 2 (PTA) 2 ] 16 (R = Ph, Et, allyl) Pd-S = 2.33-2.34 Å, cis-[Pd{SCN 4 (R)} 2 (L-L)](R = Ph, Me, Et, allyl) L-L = dppe, dppp, 6 Pd-S = 2.36-2.40 Å; L-L = bpy, dmphen, 8 Pd-S = 2.29-2.30 Å), and anionic [PdS{CN 4 (Me) 4 } 2À (Pd-S = 2.33-2.34 Å). 27 The bond length in complex 4 located in the trans position of the ethyl group is slightly longer than those of other tetrazole-thiolates, indicating a weaker trans influence of the ethyl group.…”