College of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
Chongqing Key Laboratory of Environmental Materials and Remediation Technologies, College of Chemistry and Environmental Engineering, Chongqing University of Arts and Sciences, Chongqing 402160, China.
Inorg Chem. 2022 Dec 19;61(50):20373-20384. doi: 10.1021/acs.inorgchem.2c03008. Epub 2022 Dec 7.
Attempted preparation of a low-valent Ca(I) complex by reduction of Ca iodide precursor [LCaI(THF)] () (L = [CHC(NAr)CHC(CH)NCHCHN(CH)], Ar = 2,6-PrCH), with KC led to isolation of a dinuclear calcium azaallyl complex {[HCC(NAr)CHC(CH)(NCHCHN(CH))]Ca(THF)} (). Alternatively, reaction of with KC in the presence of azobenzene gives an azobenzenyl calcium complex LCa(PhNNPh)(THF) (). The electron paramagnetic resonance and UV-vis spectra of complex suggest that the (PhNNPh) moiety should be regarded as a radical anion. Complex can react with MeSiN, MeSiCHN, CS, W(CO), elemental sulfur, and AgBr, resulting in the formation of the azido complex [LCaN(THF)] (), isonitril complex {LCa[CNN(Si(CH))]} (), dimeric bis(thiolate) complex {[SCC(CMe(NAr))C(Me)NCHCHNMe]Ca(DME)} (), metallocyclic carbene complex {[OC(W(CO))N(CH)]Ca(THF)} (), bis(thiolate) complex {[SC(CMe(NAr))C(Me)NCHCHNMe]Ca(THF)} (), and bromide complex [LCaBr(THF)] (). Additional insights on the reaction process resulting in the formation of complex are provided by density-functional theory studies. These results demonstrate that the (PhNNPh) radical anion can serve as a very potent one-electron donor, and acts as a low-valent calcium(I) synthon.
尝试通过还原碘化钙前体 [LCaI(THF)] () (L = [CHC(NAr)CHC(CH)NCHCHN(CH)], Ar = 2,6-PrCH)来制备低价钙(I)配合物，与 KC 反应导致二核钙氮杂烯丙基配合物 {[HCC(NAr)CHC(CH)(NCHCHN(CH))]Ca(THF)} ()的分离。或者，与 KC 在偶氮苯存在下反应，得到偶氮苯基钙配合物 LCa(PhNNPh)(THF) ()。配合物 的电子顺磁共振和紫外可见光谱表明，(PhNNPh)部分应被视为自由基阴离子。配合物 可与 MeSiN、MeSiCHN、CS、W(CO)、元素硫和 AgBr 反应，形成叠氮化物配合物 [LCaN(THF)] ()、异腈配合物 {LCa[CNN(Si(CH))]} ()、二硫代配合物 {[SCC(CMe(NAr))C(Me)NCHCHNMe]Ca(DME)} ()、金属环卡宾配合物 {[OC(W(CO))N(CH)]Ca(THF)} ()、二硫代配合物 {[SC(CMe(NAr))C(Me)NCHCHNMe]Ca(THF)} ()和溴化物配合物 [LCaBr(THF)] ()。密度泛函理论研究提供了对形成配合物 反应过程的进一步了解。这些结果表明，(PhNNPh)自由基阴离子可以作为非常有效的单电子供体，而 充当低价钙(I)前体。
