Hydrolysis of unactivated esters and acetonitrile hydration by a hydroxo-dicopper(II) complex

被引：41

作者：

Frey, ST

Murthy, NN

Weintraub, ST

Thompson, LK

Karlin, KD

机构：

[1] JOHNS HOPKINS UNIV, DEPT CHEM, BALTIMORE, MD 21218 USA

[2] UNIV TEXAS, HLTH SCI CTR, DEPT PATHOL, SAN ANTONIO, TX 78284 USA

[3] MEM UNIV NEWFOUNDLAND, ST JOHNS, NF A1B 3X7, CANADA

来源：

INORGANIC CHEMISTRY | 1997年 / 36卷 / 06期

关键词：

D O I：

10.1021/ic961439o

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Binuclear metal-hydroxide centers are implicated in many protein hydrolases. Here, we show that the binucleating ligand N,N,N',N'-tetrakis(2-pyridylmethyl)-1,3-diamino-2-propanol (L-OH) reacts with 2 equiv of Cu-I and O-2, giving the tetranuclear complex [Cu-4(L-O-)(2)(mu-OH-)(2)](4+) (1) (X-ray), established to give binuclear species 2 upon dissolution in CH3CN. Labeling experiments show that the hydroxide moiety in 2 acts as a nucleophile for the efficient hydrolysis of unactivated acetate esters, yielding the mu-acetato-bridged complexes 3. Species 2 also slowly hydrates acetonitrile, yielding the mu-amidate-dicopper(II) complex 4.

引用

收藏

页码：956 / +

页数：3

相关论文

共 21 条

[1] SELECTIVE HYDROLYSIS OF PHOSPHATE-ESTERS, NITROPHENYL PHOSPHATES AND UPU, BY DIMERIC ZINC-COMPLEXES DEPENDS ON THE SPACER LENGTH [J].

CHAPMAN, WH ;

BRESLOW, R .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (20) :5462-5469

[2] RATE-DETERMINING COMPLEXATION IN CATALYTIC HYDROLYSIS OF UNACTIVATED ESTERS IN NEUTRAL WATER [J].

CHIN, J ;

BANASZCZYK, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (07) :2724-2726

[3] A HIGHLY EFFICIENT COPPER(II) COMPLEX CATALYZED-HYDROLYSIS OF METHYL ACETATE AT PH 7.0 AND 25-DEGREES-C [J].

CHIN, J ;

JUBIAN, V .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1989, (13) :839-841

[4] DEVELOPING ARTIFICIAL HYDROLYTIC METALLOENZYMES BY A UNIFIED MECHANISTIC APPROACH [J].

CHIN, J .

ACCOUNTS OF CHEMICAL RESEARCH, 1991, 24 (05) :145-152

[5] Manganese enzymes with binuclear active sites [J].

Dismukes, GC .

CHEMICAL REVIEWS, 1996, 96 (07) :2909-2926

[6] BINUCLEAR METAL-COMPLEXES AS EFFICIENT INTERMEDIARIES IN BIOCHEMICALLY RELEVANT HYDROLYSIS REACTIONS [J].

GOBEL, MW .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (11) :1141-1143

[7] Synthesis, reactions and structure of a hydroxo-bridged dinuclear Zn(II) complex: Modeling the hydrolytic zinc enzymes [J].

Gultneh, Y ;

Allwar ;

Ahvazi, B ;

Blaise, D ;

Butcher, RJ ;

Jasinski, J ;

Jasinski, J .

INORGANICA CHIMICA ACTA, 1996, 241 (02) :31-38

[8] SYNTHESIS, CHARACTERIZATION, AND REVERSIBLE OXYGENATION OF MU-ALKOXO DIIRON(II) COMPLEXES WITH THE DINUCLEATING LIGAND N,N,N',N'-TETRAKIS((6-METHYL-2-PYRIDYL)METHYL)-1,3-DIAMINOPROPAN-2-OLATE [J].

HAYASHI, Y ;

KAYATANI, T ;

SUGIMOTO, H ;

SUZUKI, M ;

INOMATA, K ;

UEHARA, A ;

MIZUTANI, Y ;

KITAGAWA, T ;

MAEDA, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (45) :11220-11229

[9] MODEL FOR THE POSSIBLE ENDOGENOUS BRIDGE IN OXY-HEMOCYANIN - A DI-MU-(OR)2-BRIDGED DICOPPER(II) COMPLEX (R = H, ALKYL) WITH LOW-ENERGY CHARGE-TRANSFER ABSORPTION [J].

KARLIN, KD ;

SANYAL, I ;

FAROOQ, A ;

JACOBSON, RR ;

SHAIKH, SN ;

ZUBIETA, J .

INORGANICA CHIMICA ACTA, 1990, 174 (01) :13-15

[10] Novel properties of cooperative dinuclear zinc(II) ions: The selective recognition of phosphomonoesters and their P-O ester bond cleavage by a new dinuclear zinc(II) cryptate [J].

Koike, T ;

Inoue, M ;

Kimura, E ;

Shiro, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (13) :3091-3099