Ruthenium(II) complexes bearing carboxylato and 2-oxocarboxylato ligands

被引：31

作者：

Müller, R ^{[1
]}

Hübner, E ^{[1
]}

Burzlaff, N ^{[1
]}

机构：

[1] Univ Konstanz, Fachbereich Chem, D-78457 Constance, Germany

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2004年 / 10期

关键词：

scorpionate ligands; ruthenium; bioinorganic chemistry; tripodal ligands;

D O I：

10.1002/ejic.200300816

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The syntheses of ruthenium(n) acetato and benzoato complexes [Ru(bdmpza)(O2CCH3)(PPh3)] (6) and [Ru(bdmpza)(O2CPh)(PPh3)] (7) [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate] are reported. The complexes 6 and 7 are synthesized in high yield from [Ru(bdmpza)Cl(PPh3)(2)] (1) and thallium acetate (2) or thallium benzoate (3). In a similar substitution reaction a benzoylformate complex [Ru(bdmpza)(O2CC(O)Ph)(PPh3)] (8) is obtained from 1 and thallium benzoylformate (4). Reaction of 6 or 7 with benzoylformic acid also yields 8. In analogous reactions several 2-oxocarboxylato ruthenium(II) complexes [Ru(bdmpza){O2CC(O)R}(PPh3)] (9: R = CH2CH2CO2H, 10: R = Me, 11: R = Et) can be obtained. The low-spin ruthenium(II) complexes 8 to 11 exhibit a purple or brownish-red colour caused by MLCT transitions and thus a HOMO-LUMO gap which is almost identical to that of high-spin 2-oxoglutarate dependent iron oxygenases. 6 crystallises as a water adduct, 6(.)H(2)O and 8 forms an acetonitrile adduct 12. Crystal structures of the water adduct 6(.)H(2)O and 8 were obtained. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

引用

页码：2151 / 2159

页数：9

共 56 条

[21] Resonance Raman studies of the Iron(II)-α-keto acid chromophore in model and enzyme complexes [J].

Ho, RYN ;

Mehn, MP ;

Hegg, EL ;

Liu, A ;

Ryle, MJ ;

Hausinger, RP ;

Que, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (21) :5022-5029

[22] AN EXTENDED HUCKEL THEORY .I. HYDROCARBONS [J].

HOFFMANN, R .

JOURNAL OF CHEMICAL PHYSICS, 1963, 39 (06) :1397-&

[23] Aerobic oxidation of methyl p-tolyl sulfide catalyzed by a remarkably labile heteroscorpionate Ru(II)-aqua complex, fac-[RuII(H2O)(dpp)(tppm)]2+ [J].

Huynh, MHV ;

Witham, LM ;

Lasker, JM ;

Wetzler, M ;

Mort, B ;

Jameson, DL ;

White, PS ;

Takeuchi, KJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (02) :308-309

[24] Synthesis and characterization of monomeric (aryloxo)iron complexes: [Fe(II)L(OAr)] and [Fe(III)L(OAr)(2)] {L=BH(3,5-Pr(2)(i)pz)(3)(-)} [J].

Ito, M ;

Amagai, H ;

Fukui, H ;

Kitajima, N ;

MoroOka, Y .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1996, 69 (07) :1937-1945

[25] REMOVAL AND RECOVERY OF ORGANIC POLLUTANTS FROM THE AQUATIC ENVIRONMENT .7. ADSORPTION OF PHENOL AND CARBOXYLIC-ACIDS ON CROSSLINKED POLY(4-VINYLPYRIDINE) [J].

KAWABATA, N ;

HIGUCHI, I ;

YOSHIDA, J .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1981, 54 (11) :3253-3258

[26] SYNTHETIC MODEL FOR DIOXYGEN BINDING-SITES OF NONHEME IRON PROTEINS - X-RAY STRUCTURE OF FE(OBZ)(MECN)(HB(3,5-IPR2PZ)3) AND RESONANCE RAMAN EVIDENCE FOR REVERSIBLE FORMATION OF A PEROXO ADDUCT [J].

KITAJIMA, N ;

FUKUI, H ;

MOROOKA, Y ;

MIZUTANI, Y ;

KITAGAWA, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (17) :6402-6403

[27] MONOMERIC CARBOXYLATE FERROUS COMPLEXES AS MODELS FOR THE DIOXYGEN BINDING-SITES IN NONHEME IRON PROTEINS - THE REVERSIBLE FORMATION AND CHARACTERIZATION OF MU-PEROXO DIFERRIC COMPLEXES [J].

KITAJIMA, N ;

TAMURA, N ;

AMAGAI, H ;

FUKUI, H ;

MOROOKA, Y ;

MIZUTANI, Y ;

KITAGAWA, T ;

MATHUR, R ;

HEERWEGH, K ;

REED, CA ;

RANDALL, CR ;

QUE, L ;

TATSUMI, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (20) :9071-9085

[28]

KUNCHEV KV, 1992, RUSS J GEN CHEM+, V62, P311

[29] Chiral ruthenium complexes with P,N-ligands derived from (S)-proline [J].

Kuznetsov, VF ;

Yap, GPA ;

Alper, H .

ORGANOMETALLICS, 2001, 20 (07) :1300-1309

[30] Oxygen activating nonheme iron enzymes [J].

Lange, SJ ;

Que, L .

CURRENT OPINION IN CHEMICAL BIOLOGY, 1998, 2 (02) :159-172

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