Multinuclear Copper(I) and Silver(I) Amidinate Complexes: Synthesis, Luminescence, and CS2 Insertion Reactivity

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• 作者：Andrew C. Lane ; Matthew V. Vollmer ; Charles H. Laber ; Doris Y. Melgarejo ; Gina M. Chiarella ; John P. Fackler ; Jr. ; Xinzheng Yang ; Gary A. Baker ; Justin R. Walensky
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：November 3, 2014
• 年：2014
• 卷：53
• 期：21
• 页码：11357-11366
• 全文大小：610K
• ISSN：1520-510X

文摘

Dinuclear Cu(I) and Ag(I) complexes, Cu₂[(2,6-Me₂C₆H₃N)₂C(H)]₂, 1, Ag₂[(2,6-Me₂C₆H₃N)₂C(H)]₂, 2, Cu₂[2,6-ⁱPr₂C₆H₃N)₂C(H)]₂, 3, and Ag₂[(2,6-ⁱPr₂C₆H₃N)₂C(H)]₂, 4, were synthesized from reactions of [Cu(NCCH₃)₄][PF₆] with Na[(2,6-R₂C₆H₃N)₂C(H)] and AgO₂CCH₃ with [Et₃NH][(2,6-R₂C₆H₃N₂C(H)], R = Me, ⁱPr. Carbon disulfide was observed to insert into the metal鈥搉itrogen bonds of 1 to produce Cu₄[CS₂(2,6-Me₂C₆H₃NC(H)鈺怤C₆H₃Me₂)]₄, 5, with a Cu₄S₈ core, which represents a rare transformation of dinuclear to tetranuclear species. Insertion is also observed with 2 and CS₂, with the product likely being polymeric, 6. With the ⁱPr-derivatives, CS₂ insertion was also observed, albeit at much slower rate, with 3 and 4 producing hexanuclear clusters, M₆[CS₂(2,6-Me₂C₆H₃NC(H)鈺怤C₆H₃Me₂)]₆, M = Cu, 7; Ag, 8. Complexes 1 and 5 display green luminescence, a feature not shared by their Ag(I) analogs nor with 3. Notably, oxygen acts as a collisional quencher of the luminescence from 1 and 5 at a rate faster than most metal-based quenchometric O₂ sensors. For example, we find that complex 1 can be rapidly and reversibly quenched by oxygen, presenting a nearly 6-fold drop in intensity upon switching from nitrogen to an aerated atmosphere. The results here provide a platform from which further group 11 amidinate reactivity can be explored.