Light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes
Light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes
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DOI：
10.1021/ic025997g
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发表时间：
2003-01-13
影响因子：
4.6
通讯作者：
Coppens, P
中科院分区：
文献类型：
--
作者：
Kovalevsky, AY;Bagley, KA;Coppens, P
用激光在低温下照射通式反式钌-二氧化硫配合物[Ru-II(NH3)(4)(SO2)X]Y，导致SO2的连锁异构化，从eta(1)-平面S键到eta(2)-侧面S键，o键SO2。固相光反应在样品结晶度保持的情况下进行。反式-[Ru-(NH3)(4)Cl(eta(1)- so2)]Cl和反式-[Ru(NH3)(4)(H2O)(eta(1)- so2)](C6H5SO3)(2)的后续研究。化学。Soc. 2002, 124, 9241-9248)，我们描述了反式-[Ru-II(NH3)(4)(SO2)X]Y配合物的光晶体学，IR， DSC和理论研究（X = Cl-， H2O或CF3COO- (TFA(-))）和许多不同的反离子（Y = Cl-, C6H5SO3-, Tos（-）或TFA(-)）。低温红外实验表明，钌配位SO2的非对称和对称拉伸振动频率分别降低了约100和165 cm（-1）。反式-SO2配体和反离子的变化使MS2的衰变温度从230 K (trans-[Ru-II(NH3)（4)(SO2)Cl]Cl）增加到276 K (trans-[Ru-II(NH3)(4)(SO2)(H2O)]（Tos)(2)）。MS2态的稳定性与反式配体提供sigma的能力和反式配体的大小有关。量子化学DFT计算表明存在第三个eta(1)- o键（01）同分异构体，两个亚稳态在基态配合物能量之上0.1-0.6 eV。
The irradiation of ruthenium-sulfur dioxide complexes of general formula trans-[Ru-II(NH3)(4)(SO2)X]Y with laser light at low temperature results in linkage isomerization Of SO2, starting with eta(1)-planar S-bound to eta(2)-Side S,O-bound SO2. The solid-state photoreaction proceeds with retention of sample crystallinity. Following work on trans-[Ru-(NH3)(4)Cl(eta(1)-SO2)]Cl and trans-[Ru(NH3)(4)(H2O)(eta(1)-SO2)](C6H5SO3)(2) (Kovalevsky, A. Y.; Bagley, K. A.; Coppens, P. J. Am. Chem. Soc. 2002, 124, 9241-9248), we describe photocrystallographic, IR, DSC, and theoretical studies of trans-[Ru-II(NH3)(4)(SO2)X]Y complexes with (X = Cl-, H2O, or CF3COO- (TFA(-))) and a number of different counterions (Y = Cl-, C6H5SO3-, Tos(-), or TFA(-)). Low temperature IR experiments indicate the frequency of the asymmetric and symmetric stretching vibrations of the Ru-coordinated SO2 to be downshifted by about 100 and 165 cm(-1), respectively. Variation of the trans-to-SO2 ligand and the counterion increases the MS2 decay temperature from 230 K (trans-[Ru-II(NH3)(4)(SO2)Cl]Cl) to 276 K (trans-[Ru-II(NH3)(4)(SO2)(H2O)](Tos)(2)). The stability of the MS2 state correlates with increasing sigma-donating ability of the trans ligand and the size of the counterion. Quantum chemical DFT calculations indicate the existence of a third eta(1)-O-bound (01) isomer, the two metastable states being 0.1-0.6 eV above the energy of the ground-state complex.