TY - JOUR
T1 - Hydrothermal and solid-state transformation of ruthenium-supported Keggin-type heteropolytungstates [XW 11O 39{Ru(II)(benzene) (H 2O)}] n- (X = P (n = 5), Si (n = 6), Ge (n = 6)) to ruthenium-substituted Keggin-type heteropolytungstates
AU - Ogo, Shuhei
AU - Miyamoto, Mayumi
AU - Ide, Yusuke
AU - Sano, Tsuneji
AU - Sadakane, Masahiro
PY - 2012/9/7
Y1 - 2012/9/7
N2 - A new pathway for the preparation of mono-ruthenium (Ru)(iii)-substituted Keggin-type heteropolytungstates with an aqua ligand, [PW 11O 39Ru(iii)(H 2O)] 4- (1a), [SiW 11O 39Ru(iii)(H 2O)] 5- (1b) and [GeW 11O 39Ru(iii)(H 2O)] 5- (1c), using [Ru(ii)(benzene)Cl 2] 2 as a Ru source was described. Compounds 1a-1c were prepared by reacting [XW 11O 39] n- (X = P, Si and Ge) with [Ru(ii)(benzene)Cl 2] 2 under hydrothermal condition and were isolated as caesium salts. Ru(benzene)-supported heteropolytungstates, [PW 11O 39{Ru(ii)(benzene)(H 2O)}] 5- (2a), [SiW 11O 39{Ru(ii)(benzene)(H 2O)}] 6- (2b) and [GeW 11O 39{Ru(ii)(benzene)(H 2O)}] 6- (2c), were first produced in the reaction media, and then transformed to 1a, 1b and 1c, respectively, under hydrothermal conditions. Calcination of Ru(benzene)-supported heteropolytungstates, 2a, 2b and 2c, in the solid state produced mixtures of 1a, 1b and 1c with CO (carbon monoxide)-coordinated complexes, [PW 11O 39Ru(ii)(CO)] 5- (4a), [SiW 11O 39Ru(ii)(CO)] 6- (4b) and [GeW 11O 39Ru(ii)(CO)] 6- (4c), respectively. From comparison of their catalytic activities in water oxidation reaction, it was indicated that ruthenium should be incorporated in the heteropolytungstate in order to promote catalytic activity.
AB - A new pathway for the preparation of mono-ruthenium (Ru)(iii)-substituted Keggin-type heteropolytungstates with an aqua ligand, [PW 11O 39Ru(iii)(H 2O)] 4- (1a), [SiW 11O 39Ru(iii)(H 2O)] 5- (1b) and [GeW 11O 39Ru(iii)(H 2O)] 5- (1c), using [Ru(ii)(benzene)Cl 2] 2 as a Ru source was described. Compounds 1a-1c were prepared by reacting [XW 11O 39] n- (X = P, Si and Ge) with [Ru(ii)(benzene)Cl 2] 2 under hydrothermal condition and were isolated as caesium salts. Ru(benzene)-supported heteropolytungstates, [PW 11O 39{Ru(ii)(benzene)(H 2O)}] 5- (2a), [SiW 11O 39{Ru(ii)(benzene)(H 2O)}] 6- (2b) and [GeW 11O 39{Ru(ii)(benzene)(H 2O)}] 6- (2c), were first produced in the reaction media, and then transformed to 1a, 1b and 1c, respectively, under hydrothermal conditions. Calcination of Ru(benzene)-supported heteropolytungstates, 2a, 2b and 2c, in the solid state produced mixtures of 1a, 1b and 1c with CO (carbon monoxide)-coordinated complexes, [PW 11O 39Ru(ii)(CO)] 5- (4a), [SiW 11O 39Ru(ii)(CO)] 6- (4b) and [GeW 11O 39Ru(ii)(CO)] 6- (4c), respectively. From comparison of their catalytic activities in water oxidation reaction, it was indicated that ruthenium should be incorporated in the heteropolytungstate in order to promote catalytic activity.
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U2 - 10.1039/c2dt30475a
DO - 10.1039/c2dt30475a
M3 - Article
C2 - 22622450
AN - SCOPUS:84864626933
VL - 41
SP - 9901
EP - 9907
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 33
ER -