Synthesis and Reactivity of a Neutral, Three‐Coordinate Platinum(II) Complex Featuring Terminal Amido Ligation

Abstract

Ac rystallographically characterized three-coordinate,f ormally 14 electron Pt II complex 1 featuring terminal amido ligation is reported. Computational analysis revealed relatively weak p donation from the amide lone pair to platinum and supports a1 4-electron assignment for 1. Stoichiometric reactivity studies confirmed the viability of net O À Ha nd C À Ha ddition across,a sw ell as isonitrile insertion into,the terminal platinum-amido linkage of 1.

Dehydrogenative B−H/C(sp3)−H Benzylic Borylation within the Coordination Sphere of Platinum(II)

“…ing low-coordinate transition metal complexes, [9] including the first isolable three-coordinate 14-electron Pt II complex featuring terminal amido ligation. [10] In building on this chemistry,w ee nvisioned that reaction of 16-electron (k 2 -P, N-1)Pt(h 3 -benzyl) (2-Pt)w ith R n EÀHb onds would, upon loss of toluene,a fford new and potentially unusual lowcoordinate (k 2 -P,N-1)Pt(ER n )c ompounds. [11] Tr eatment of the N-phosphinoamidine 1[H] with (COD)PtCl(benzyl), followed by exposure to base afforded the N-phosphinoamidinate complex 2-Pt in 73 %i solated yield (Scheme 2).…”

Dehydrogenative B−H/C(sp3)−H Benzylic Borylation within the Coordination Sphere of Platinum(II)

“…We have reported previously on the utility of the monoanionic N ‐phosphinoamidinate P,N ligand 1 in supporting low‐coordinate transition metal complexes, including the first isolable three‐coordinate 14‐electron Pt II complex featuring terminal amido ligation . In building on this chemistry, we envisioned that reaction of 16‐electron (κ 2 ‐P,N‐ 1 )Pt(η 3 ‐benzyl) ( 2‐Pt ) with R n E−H bonds would, upon loss of toluene, afford new and potentially unusual low‐coordinate (κ 2 ‐P,N‐ 1 )Pt(ER n ) compounds .…”