Hadzovic Alen, Song Datong
Davenport Chemical Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, Canada, M5S 3H6.
Inorg Chem. 2008 Dec 15;47(24):12010-7. doi: 10.1021/ic801557c.
The reaction between (Ar(2)nacnac)H (Ar = C(6)H(5), ligand a; 2,6-((i)Pr)(2)C(6)H(3), ligand b) and [Pd(OAc)(2)] produces red complexes [Pd(Ar(2)nacnac)(OAc)] (1a: Ar = C(6)H(5); 1b: Ar = 2,6-((i)Pr)(2)C(6)H(3)). Complex 1a has a dimeric structure in the solid state with two bridging acetates, while a monomer-dimer equilibrium establishes in solution. Complex 1b is monomeric in both the solid state and solution. Both are air- and moisture-stable compounds, unlike [Pd(Ph(2)nacnac)(2)] (2), which easily hydrolyzes in the presence of moisture to give [Pd(Phnacac)(2)] (3) (Phnacac = {CH(3)C(NPh)CHC(O)CH(3)}(-)). Compound 1a reacts with metal acetates to produce heterotrimetallic complexes of a general formula Pd(Ph(2)nacnac)-mu-[M(OAc)(4)] (4, M = Cu; 5, M = Zn). Treating 1a with KOH in THF, or alternatively Pd(Ph(2)nacnac)Cl with KO(t)Bu in wet THF, produces Pd(Ph(2)nacnac)(OH) (6).
(Ar(2)nacnac)H（Ar = C(6)H(5)，配体a；2,6-((i)Pr)(2)C(6)H(3)，配体b）与[Pd(OAc)(2)]反应生成红色配合物[Pd(Ar(2)nacnac)(OAc)]（1a：Ar = C(6)H(5)；1b：Ar = 2,6-((i)Pr)(2)C(6)H(3)）。配合物1a在固态时具有二聚体结构，含有两个桥连乙酸根，而在溶液中则建立起单体 - 二聚体平衡。配合物1b在固态和溶液中均为单体。与[Pd(Ph(2)nacnac)(2)]（2）不同，这两种配合物都是对空气和湿气稳定的化合物，[Pd(Ph(2)nacnac)(2)]在湿气存在下容易水解生成[Pd(Phnacac)(2)]（3）（Phnacac = {CH(3)C(NPh)CHC(O)CH(3)}(-)）。化合物1a与金属乙酸盐反应生成通式为Pd(Ph(2)nacnac)-μ-[M(OAc)(4)]的异三金属配合物（4，M = Cu；5，M = Zn）。在四氢呋喃中用氢氧化钾处理1a，或者在湿四氢呋喃中用叔丁醇钾处理Pd(Ph(2)nacnac)Cl，可生成Pd(Ph(2)nacnac)(OH)（6）。
