New Cationic and Zwitterionic Cp*M(κ<sup>2</sup>-P,S) Complexes (M = Rh, Ir): Divergent Reactivity Pathways Arising from Alternative Modes of Ancillary Ligand Participation in Substrate Activation
作者:Kevin D. Hesp、Robert McDonald、Michael J. Ferguson、Mark Stradiotto
DOI:10.1021/ja8062277
日期:2008.12.3
[Cp'Ir(kappa(2)-P,S)](+)X(-) complexes. Exposure of [2](+)OTf(-) to CO afforded [2 x CO](+)OTf(-) in 91% yield, while treatment of [2](+)B(C(6)F(5))(4)(-) with PMe(3) generated [2 x PMe(3)](+)B(C(6)F(5))(4)(-) in 94% yield. Treatment of 1 with K(2)CO(3) in CH(3)CN allowed for the isolation of the unusual adduct 3 x CH(3)CN (41% isolated yield), in which the CH(3)CN bridges the Lewis acidic Cp*Ir and Lewis
用 1/3-P(i)Pr(2)-2-S(t)Bu-茚处理 0.5 当量的 [Cp*IrCl(2)](2) 得到 Cp*Ir(Cl)(kappa(2) )-3-P(i)Pr(2)-2-S-茚) (1),产率为 95% (Cp* = eta(5)-C(5)Me(5))。将 AgOTf 或 LiB(C(6)F(5))(4) x 2.5 OEt(2) 添加到 1 得到 [Cp*Ir(kappa(2)-3-P(i)Pr(2)-2- S-茚)](+)X(-) ([2](+)X(-); X = OTf, 78%; X = B(C(6)F(5))(4), 82% ),它们代表了可分离配位不饱和 [Cp'Ir(kappa(2)-P,S)](+)X(-) 复合物的第一个例子。[2](+)OTf(-) 暴露于 CO 以 91% 的产率提供 [2 x CO](+)OTf(-),而处理 [2](+)B(C(6)F(5)
(κ2-P,S)Pt(benzyl) complexes derived from 1/3-PiPr2-2-StBu-indene: facile synthesis of carbanion- and borate-containing zwitterions
作者:Kevin D. Hesp、Robert McDonald、Michael J. Ferguson、Gabriele Schatte、Mark Stradiotto
DOI:10.1039/b813421a
日期:——
The versatile new ligand precursor 1/3-P(i)Pr(2)-2-S(t)Bu-indene has been employed in the preparation of neutral and cationic (kappa(2)-P,S)Pt(benzyl) complexes, as well as structurally related zwitterions in which the formally cationic metal fragment is counterbalanced by an uncoordinated indenide or borate fragment that is contained within the ancillary ligand backbone.