Multinuclear silver(I) XPhos complexes with cyclooctatetraene: photochemical C-C bond cleavage of acetonitrile and cyanide bridged Ag cluster formation

Grirrane A.; Alvarez E.; Albero J.; Garcia H.; Corma A.

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Multinuclear silver(I) XPhos complexes with cyclooctatetraene: photochemical C-C bond cleavage of acetonitrile and cyanide bridged Ag cluster formation

机译：多环环辛烯银（I）XPhos配合物：乙腈和氰化物桥联的Ag团簇形成的光化学C-C键裂解

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Cationic mono-, di-, tri-and tetra-nuclear silver complexes with Buchwald-type phosphane (XPhos) and cyclooctatetraene (COT) have been synthesized and characterized. Formation of [(XPhos-Ag) n(COT)][SbF6](n) (n = 1 and 2) complexes was confirmed by single-crystal X-ray crystallography and multinuclear NMR spectroscopy. Variable-temperature NMR spectroscopy in CD2Cl2 solution shows the fluxionality of the COT ring in the mono-Ag(I) XPhos complex. Fluxionality of COT was also confirmed in the case of the di-Ag(I) XPhos complex by solid-state and solution P-31 NMR spectroscopy. The C-C bond cleavage of coordinated acetonitrile [XPhos-Ag(I)-NCCH3] resulting in cyanide bridged Ag cluster formation [(XPhos-Ag)(2)(mu-CN)(n)(mu-Ag)(n-1)] (n = 1, 2, 3 and 4) upon light excitation of [(XPhos-Ag)(n)(COT)] was confirmed by HRESI-MS, UV-Absorption and HR-TEM.

机译：已合成和表征了具有布赫瓦尔德型膦（XPhos）和环辛酸酯（COT）的阳离子单，二，三和四核银配合物。 [（XPhos-Ag）n（COT）] [SbF6]（n）（n = 1和2）配合物的形成已通过单晶X射线晶体学和多核NMR光谱证实。 CD2Cl2溶液中的可变温度NMR光谱显示了单Ag（I）XPhos络合物中COT环的流动性。在di-Ag（I）XPhos配合物的情况下，固态和溶液P-31 NMR光谱也证实了COT的流动性。配位乙腈[XPhos-Ag（I）-NCCH3]的CC键裂解导致氰化物桥接的Ag簇形成[（XPhos-Ag）（2）（mu-CN）（n）（mu-Ag）（n-1） HRESI-MS，UV吸收和HR-TEM证实了[（XPhos-Ag）（n）（COT）]的光激发后的）]（n = 1、2、3和4）。

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《Dalton transactions: An international journal of inorganic chemistry》 |2016年第13期|共7页
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Grirrane A.; Alvarez E.; Albero J.; Garcia H.; Corma A.;
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1. Multinuclear silver(I) XPhos complexes with cyclooctatetraene: photochemical C-C bond cleavage of acetonitrile and cyanide bridged Ag cluster formation [J] . Grirrane A., Alvarez E., Albero J., Dalton transactions: An international journal of inorganic chemistry . 2016,第13期

机译：多环环辛烯银（I）XPhos配合物：乙腈和氰化物桥联的Ag团簇形成的光化学C-C键裂解
2. C-C bond cleavage in acetonitrile by copper(ii)-bipyridine complexes and in situ formation of cyano-bridged mixed-valent copper complexes [J] . Xu F., Tao T., Zhang K., Dalton transactions: An international journal of inorganic chemistry . 2013,第10期

机译：铜（ii）-联吡啶配合物在乙腈中裂解C-C键并原位形成氰基桥联的混合价铜配合物
3. Novel cyano-bridged mixed-valent copper complexes formed by completely in situ synthetic method via the cleavage of C-C bond in acetonitrile [J] . Xu F., Huang W., You X.-Z. Dalton transactions: An international journal of inorganic chemistry . 2010,第44期

机译：通过完全原位合成方法通过裂解乙腈中的C-C键形成的新型氰基桥联混合价铜络合物
4. Mechanistic Insights on C-C Bond Cleavage, C-O Bond Cleavage, and Hydrogen Insertion in Light Carboxylic Acids Catalyzed by Dispersed Ruthenium Clusters in Aqueous Medium [C] . Junnan Shangguan, Ya-Huei (Cathy) Chin AIChE Annual Meeting . 2015

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5. Catalytic C-C (C-N) Bond Formation and C-O Bond Cleavage by Pincer-Ligated Iridium Complexes [D] . Li, Bo. 2019

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6. Graphene-catalyzed formation of C≡N bonds via cleavage of C-C and N-O bonds in ethanol and nitrate under room temperature [O] . Ding Xiao, Wucong Wang, Yanzhe Gai, -1

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7. Direct cyanidation of silver sulfide by heterolytic C–CN bond cleavage of acetonitrile [O] . Biraj Das, Pinku Saikia, Mukesh Sharma, 2020

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8. Transition-Metal Mediated Formation and Cleavage of Carbon-Hydrogen Bonds: Hydrogenolysis of Trinuclear Alkylidyne Clusters and Oxidative Addition of Carbon-Hydrogen Bonds to Rhenium [R] . Seidler, P. F. 1985

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Multinuclear silver(I) XPhos complexes with cyclooctatetraene: photochemical C-C bond cleavage of acetonitrile and cyanide bridged Ag cluster formation

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