Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes - A photocrystallographic investigation

Warren M.R.; Brayshaw S.K.; Hatcher L.E.; Johnson A.L.; Schiffers S.; Warren A.J.; Teat S.J.; Warren J.E.; Woodall C.H.; Raithby P.R.

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Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes - A photocrystallographic investigation

机译：镍，钯和铂二硝基配合物单晶中的光活化键合异构现象-光学晶体学研究

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Low temperature, single crystal photocrystallographic studies have been carried out on four square planar Group 10 complexes [Ni(PEt_3)_2(NO_2)_2] 1, [Pd(PPh_3)_2(NO_2)_2]2, [Pd(AsPh_3)_2(NO_2)_2] 3 and [Pt(PPh_3)_2(NO_2)_2] 4, in which the two nitro groups adopt the trans configuration. Irradiation with UV light, at 100 K, of single crystals of complexes 1-3 photoisomerise from the η ~1-NO_2 nitro form to the η 1-ONO nitrito form occurred. Complex 1 underwent 25% conversion to the nitrito form before crystal decomposition occurred. 2 and 3 underwent 46% and 39% conversion, respectively, to the nitrito form when a photostationary state was reached. While under the same experimental conditions 4 showed no isomerisation. The photocrystallographic results can be correlated with the results of DFT calculations and with the observed trends in the solution UV/visible absorption spectroscopy obtained for these complexes. The results suggest that while steric factors in the isomerization processes are important there may also be a kinetic effect relating to the lability of the metal involved.

机译：低温单晶光晶体学研究已在四个方形平面10组络合物[Ni（PEt_3）_2（NO_2）_2] 1，[Pd（PPh_3）_2（NO_2）_2] 2，[Pd（AsPh_3）_2 （NO_2）_2] 3和[Pt（PPh_3）_2（NO_2）_2] 4，其中两个硝基均采用反式构型。用紫外光在100 K下照射了从η〜1-NO_2硝基形式到η1-ONO亚硝基形式的配合物1-3光异构化的单晶。在晶体分解发生之前，配合物1经历了25％转化为亚硝基形式。当达到光稳态时，图2和图3分别转化为亚硝基形式的转化率为46％和39％。虽然在相同的实验条件下4没有显示异构化。可以将光结晶学结果与DFT计算的结果以及对于这些络合物获得的溶液UV /可见吸收光谱的观察趋势相关联。结果表明，尽管异构化过程中的空间因素很重要，但也可能存在与所涉及金属的不稳定性有关的动力学效应。

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《Dalton transactions: An international journal of inorganic chemistry》 |2012年第42期|共7页
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Warren M.R.; Brayshaw S.K.; Hatcher L.E.; Johnson A.L.; Schiffers S.; Warren A.J.; Teat S.J.; Warren J.E.; Woodall C.H.; Raithby P.R.;
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1. Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes - A photocrystallographic investigation [J] . Warren M.R., Brayshaw S.K., Hatcher L.E., Dalton transactions: An international journal of inorganic chemistry . 2012,第42期

机译：镍，钯和铂二硝基配合物单晶中的光活化键合异构现象-光学晶体学研究
2. Linkage isomerism in 4-(2-aminoethyl)morpholine (L) complexes of nickel (II) nitrite: X-ray single crystal structure of trans-[NiL2(NO2)(2)] [J] . Chattopadhyay T, Ghosh M, Majee A, Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 2005,第13期

机译：亚硝酸镍（II）的4-（2-氨基乙基）吗啉（L）配合物中的键合异构现象：反式[NiL2（NO2）（2）]的X射线单晶结构
3. First report on thermally induced nitro->nitrito(O,O)linkage isomerization in diamine complexes of nickel(II) in the solid state: X-ray single crystal structural analyses of nitro and nitrito isomers [J] . Inamur Rahaman Laskar, Debasis Das, Goalm Mostafa, New Journal of Chemistry . 2001,第5期

机译：固态镍（II）的二胺络合物中热诱导硝基->腈（O，O）链异构化的首次报道：硝基和亚硝基异构体的X射线单晶结构分析
4. Monitoring of the ultrafast vibrational kinetic during formation of photo-induced linkage isomers in Na_2Fe(CN)_5NO·2H_2O single crystal [C] . G. Galle, M. Nicoul, Th. Woike, International Conference on Ultrafast Phenomena . 2013

机译：在Na_2 Fe（CN）_5nO·2H_2O单晶中形成光诱导的连杆异构体期间超快振动动力学的监测
5. Synthesis and investigation of square planar bis(ferrocenyl) dithiolene complexes of nickel, palladium, and platinum: Control of near-infrared absorption and other properties by ligand modification. [D] . Sanders, Richard West, Jr. 2002

机译：镍，钯和铂的方形平面双（二茂铁基）二硫辛烯络合物的合成和研究：通过配体修饰控制近红外吸收和其他性质。
6. Multiple light-induced NO linkage isomers in the dinitrosyl complex RuCl(NO)2(PPh3)2BF4 unravelled by photocrystallographic and IR analysis [O] . Nicolas Casaretto, Sebastien Pillet, El Eulmi Bendeif, 2015

机译：光结晶和红外分析揭示二亚硝酰基络合物RuCl（NO）2（PPh3）2 BF4中的多种光诱导NO键合异构体
7. Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes: A photocrystallographic investigation [O] . Warren M.R., Brayshaw S.K., Hatcher L.E., 2012

机译：镍，钯和铂二硝基配合物单晶中的光活化键合异构体：光结晶学研究
8. New Trifluorosilyl Exchange Reagent: Reactions of Cd(SiF3)2.glyme (glyme = dimethoxyethane) with Dibromo Metal Phosphine Complexes of Platinum, Palladium, and Nickel yield Trifluorosilyl Substituted Dialkyl Compounds. [R] . Guerra, M. A., Lagow, R. J. 1990

机译：新的三氟甲硅烷基交换试剂：Cd（siF3）2甘氨酸（甘醇二甲醚=二甲氧基乙烷）与铂，钯和镍的二溴金属膦配合物的反应产生三氟甲硅烷基取代的二烷基化合物。

Photoactivated linkage isomerism in single crystals of nickel, palladium and platinum di-nitro complexes - A photocrystallographic investigation

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