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Divergent Solution and Solid-State Structures of Mono- and Dinuclear Nickel(II) Pyridone Complexes
Organometallics ( IF 2.5 ) Pub Date : 2020-02-25 , DOI: 10.1021/acs.organomet.9b00799 Sean T. Goralski 1 , Taylor A. Manes 1 , Simone E. A. Lumsden 1 , Vincent M. Lynch 1 , Michael J. Rose 1
Organometallics ( IF 2.5 ) Pub Date : 2020-02-25 , DOI: 10.1021/acs.organomet.9b00799 Sean T. Goralski 1 , Taylor A. Manes 1 , Simone E. A. Lumsden 1 , Vincent M. Lynch 1 , Michael J. Rose 1
Affiliation
The chelating 2-pyridone ligand (E)-6-(1-((2-(methylthio)phenyl)imino)ethyl)pyridin-2(1H)-one (1) has been used to synthesize five nickel(II) complexes that have been characterized by single-crystal X-ray diffraction, UV/vis and IR spectroscopies, and benchtop magnetometry. Reaction of NiX2 (X = BF4, Cl) with 1 yielded the C2-symmetric halide-bridged Ni dimers [(μ-F)Ni2(κN,N,O-1–)2(κN,N-1)2](BF4) (2) and [(μ-Cl)Ni2(κN,N,O-1–)2(κN,N-1–)(κN,N-1)] (3), where 2 is formed via a rare example of fluoride abstraction from BF4– by a transition metal. Remarkably, the reaction of Ni(OAc)2 with 1 followed by different methods of crystallization yielded three different products: the dimer [(μ-OH2)Ni2(κN,N,O-1–)(κN,N-1–)(κN,N-1)(OAc)2] (4), as well as the monomers [Ni(κN,N-1–)2(MeOH)2] (5) and [Ni(κN,N-1–)(κN,N-1)(OAc)(OH2)] (6). This observation is emblematic of the soft energy landscape of coordination motifs and nuclearity that pyridone ligands provide with late 3d transition metals. To better understand the solution versus solid-state speciation, solid-state UV/vis reflectance and solution-state UV/vis absorbance spectra were obtained. Surprisingly, the solution-state UV/vis spectra of 4 and 6 each provided nearly identical absorption spectra (λmax ≈ 360 nm), which matched neither of the solid-state reflectance spectra of 4 or 6 (λ ≈ 590, 790, 970 nm; 3A2g → 3T1g, 3A2g→1E2g, and 3A2g → 3T2g, respectively). Rather, the solution spectra are consistent only with the spectroscopic features (MLCT) of a conventional square-planar Ni(II) species.
中文翻译:
单核和双核镍吡啶酮配合物的发散溶液和固态结构
螯合的2-吡啶酮配体(E)-6-(1-(((2-(甲硫基苯基)亚氨基)乙基)吡啶-2-2(1 H)-一(1)已用于合成五个镍(II)配合物的特征在于单晶X射线衍射,UV / vis和IR光谱学以及台式磁力计。NIX的反应2(X = BF 4与,Cl)的1,得到Ç 2 -对称卤化物桥连的Ni二聚体[(μ-F)的Ni 2(κN,Ñ,ö - 1 - )2(κ Ñ,ñ - 1)2 ](BF 4)(2)和[(μ-Cl)的镍2(κ Ñ,Ñ,ö - 1 - )2(κ Ñ,ñ - 1 - )(κ Ñ,ñ - 1)](3),其中,2是通过从BF氟化物抽象的一个罕见的例子形成4 -由过渡金属。值得注意的是,Ni(OAc)2与1的反应以及随后不同的结晶方法产生了三种不同的产物:二聚体[(μ-OH 2)的Ni 2(κ Ñ,Ñ,ö - 1 - )(κ Ñ,ñ - 1 - )(κ Ñ,ñ - 1)(OAc)2 ](4),以及的单体[镍(κ ñ,ñ - 1 - )2(甲醇)2 ](5)和[镍(κ ñ,ñ - 1 - )(κ ñ,N - 1)(OAc)(OH 2)](6)。该观察结果象征了吡啶酮配体与晚期3d过渡金属一起提供的配位基序和核能的软能态势。为了更好地理解溶液与固态形态之间的关系,获得了固态UV / vis反射率和溶液态UV / vis吸收光谱。出人意料的是,溶液状态的UV / VIS光谱4和6的每个提供几乎相同的吸收光谱(λ最大≈360纳米),其匹配既不的固态反射光谱的4或6(λ≈590,790,970 nm; 3 A 2克→3 T 1g,3 A 2g →1 E 2g和3 A 2g → 3 T 2g)。相反,溶液光谱仅与常规方平面Ni(II)物种的光谱特征(MLCT)一致。
更新日期:2020-02-25
中文翻译:
单核和双核镍吡啶酮配合物的发散溶液和固态结构
螯合的2-吡啶酮配体(E)-6-(1-(((2-(甲硫基苯基)亚氨基)乙基)吡啶-2-2(1 H)-一(1)已用于合成五个镍(II)配合物的特征在于单晶X射线衍射,UV / vis和IR光谱学以及台式磁力计。NIX的反应2(X = BF 4与,Cl)的1,得到Ç 2 -对称卤化物桥连的Ni二聚体[(μ-F)的Ni 2(κN,Ñ,ö - 1 - )2(κ Ñ,ñ - 1)2 ](BF 4)(2)和[(μ-Cl)的镍2(κ Ñ,Ñ,ö - 1 - )2(κ Ñ,ñ - 1 - )(κ Ñ,ñ - 1)](3),其中,2是通过从BF氟化物抽象的一个罕见的例子形成4 -由过渡金属。值得注意的是,Ni(OAc)2与1的反应以及随后不同的结晶方法产生了三种不同的产物:二聚体[(μ-OH 2)的Ni 2(κ Ñ,Ñ,ö - 1 - )(κ Ñ,ñ - 1 - )(κ Ñ,ñ - 1)(OAc)2 ](4),以及的单体[镍(κ ñ,ñ - 1 - )2(甲醇)2 ](5)和[镍(κ ñ,ñ - 1 - )(κ ñ,N - 1)(OAc)(OH 2)](6)。该观察结果象征了吡啶酮配体与晚期3d过渡金属一起提供的配位基序和核能的软能态势。为了更好地理解溶液与固态形态之间的关系,获得了固态UV / vis反射率和溶液态UV / vis吸收光谱。出人意料的是,溶液状态的UV / VIS光谱4和6的每个提供几乎相同的吸收光谱(λ最大≈360纳米),其匹配既不的固态反射光谱的4或6(λ≈590,790,970 nm; 3 A 2克→3 T 1g,3 A 2g →1 E 2g和3 A 2g → 3 T 2g)。相反,溶液光谱仅与常规方平面Ni(II)物种的光谱特征(MLCT)一致。