TY - JOUR
T1 - Light-induced metastable linkage isomers of ruthenium sulfur dioxide complexes
AU - Kovalevsky, Andrey Yu
AU - Bagley, Kimberly A.
AU - Cole, Jacqueline M.
AU - Coppens, Philip
PY - 2003/1
Y1 - 2003/1
N2 - The irradiation of ruthenium-sulfur dioxide complexes of general formula trans-[RuII(NH3)4(SO2)X]Y with laser light at low temperature results in linkage isomerization of SO2, starting with η1-planar S-bound to η2-Side S,O-bound SO2. The solid-state photoreaction proceeds with retention of sample crystallinity. Following work on trans-[Ru- (NH3)4Cl(η1-SO2)]Cl and trans-[Ru(NH3)4(H2O) (η1-SO2)](C6H5 SO3)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-[RuII(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-[RuII(NH3)4(SO2)Cl]Cl) to 276 K (trans-[RuII(NH3)4 (SO2)(H2O)](Tos)2). The stability of the MS2 state correlates with increasing σ-donating ability of the trans ligand and the size of the counterion. Quantum chemical DFT calculations indicate the existence of a third η1-O-bound (MS1) isomer, the two metastable states being 0.1-0.6 eV above the energy of the ground-state complex.
AB - The irradiation of ruthenium-sulfur dioxide complexes of general formula trans-[RuII(NH3)4(SO2)X]Y with laser light at low temperature results in linkage isomerization of SO2, starting with η1-planar S-bound to η2-Side S,O-bound SO2. The solid-state photoreaction proceeds with retention of sample crystallinity. Following work on trans-[Ru- (NH3)4Cl(η1-SO2)]Cl and trans-[Ru(NH3)4(H2O) (η1-SO2)](C6H5 SO3)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-[RuII(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-[RuII(NH3)4(SO2)Cl]Cl) to 276 K (trans-[RuII(NH3)4 (SO2)(H2O)](Tos)2). The stability of the MS2 state correlates with increasing σ-donating ability of the trans ligand and the size of the counterion. Quantum chemical DFT calculations indicate the existence of a third η1-O-bound (MS1) isomer, the two metastable states being 0.1-0.6 eV above the energy of the ground-state complex.
UR - http://www.scopus.com/inward/record.url?scp=0037243531&partnerID=8YFLogxK
U2 - 10.1021/ic025997g
DO - 10.1021/ic025997g
M3 - Article
C2 - 12513088
AN - SCOPUS:0037243531
SN - 0020-1669
VL - 42
SP - 140
EP - 147
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 1
ER -