1,2-H SHIFT ON TETRANUCLEAR ETHYNYL COMPLEXES (MU(4)-C2H)(ETA(5)-C(5)R(5))FEMCO(2)(CO)(N) (M=FE, RU N=10,11 R=H, ME)

被引：18

作者：

AKITA, M

HIRAKAWA, H

SAKAKI, K

MOROOKA, Y

机构：

[1] Research Laboratory of Resources Utilization, Tokyo Institute of Technology, Midori-ku, Yokohama 226

来源：

ORGANOMETALLICS | 1995年 / 14卷 / 06期

关键词：

D O I：

10.1021/om00006a025

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The interaction of the trinuclear ethynyl complexes Co-2(CO)(6)[mu-(eta(5)-C(5)R(5))Fe(CO)(2)C=CH] (3: a, R = H; b, R = Me] with Fe-2(CO)(9) and the addition reaction of (eta(5)-C(5)R(5))Fe(CO)(2)C=CH (1a,b) to the trimetallic species RuCo2(CO)(11) afford the tetranuclear vinylidene intermediates Co(2)M(CO)(9)[mu(3)-C=C(H)Fe(eta(5)-C(5)R(5))(CO)(2)] (4, M = Fe; 6, M = Ru), respectively, which are thermally decarbonylated to produce the tetranuclear acetylide clusters (mu(4)-C2H)[(eta(5)-C(5)R(5))Fe]MCo(2)(CO)(10) (5, M = Fe; 7, M = Ru) with the spiked triangular metal array. The skeletal rearrangement [HC=CFe (1, 3) --> C=C(H)Fe (4, 6) --> HC=CFe (5, 7)1 can be explained in terms of a 1,2-H shift on the Ca bridge of the plausible alkyne-cluster type intermediates [mu(3)-(eta(5)-C(5)R(5))Fe(CO)(2)C=CH]MCo(2)(CO)(9) [M = Fe (9), Ru (10)].

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页码：2775 / 2780

页数：6

相关论文

共 35 条

[1] UNUSUAL REACTIVITIES OF (MU-ETA-2-ETA-2-FP-C-EQUIVALENT-TO-C-H)CO2(CO)6, THE ADDUCTS OF FP-C-EQUIVALENT-TO-C-H TO CO2(CO)8 - PHOTOLYSIS, THERMOLYSIS AND REDUCTION WITH HYDROSILANES GIVING POLYNUCLEAR COMPLEXES, (CP)2FE2CO3(MU-5-C=CH)(CO)10, (MU-CH=CH)[(-MU-3-C)CO3(CO)9]2 AND CPFECO3(MU-C=CH2)(CO)9 [J].

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[2] SYNTHESIS AND CHARACTERIZATION OF (CP)2MO2(CO)4(MU-ETA-2-ETA-2-FP-C=C-H), ADDUCTS OF ETHYNYLIRON COMPLEXES TO (CP)2MO2(CO)4 - THEIR FLUXIONAL BEHAVIOR VIA REVERSIBLE 1-ALKYNE-VINYLIDENE LIGAND INTERCONVERSION ON A DINUCLEAR SYSTEM AND PHOTOCHEMICAL DECARBONYLATION LEADING TO THE MU-3-VINYLIDENYL COMPLEXES (CP)FECP2MO2(CO)4(MU-CO)(MU-=C=CH) [J].

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[3] TRANSFORMATION OF THE C2H LIGAND IN FP-ASTERISK-C-EQUIVALENT-TO-CH (FP-ASTERISK=(ETA-5-C5ME5)FE(CO)2) INTO VARIOUS C-2 FUNCTIONAL-GROUPS VIA AN IRON-SUBSTITUTED MANGANESE VINYLIDENE COMPLEX, (ETA-5-C5H4ME)MN(CO)2[=C=C(H)FP-ASTERISK] - ITS AMPHOTERIC REACTIVITIES, STRUCTURAL COMPARISONS RELEVANT TO 1-ALKYNE-TO-VINYLIDENE REARRANGEMENTS, AND ELECTRONIC INFLUENCES ON STRUCTURES OF HETEROBIMETALLIC BRIDGING ALKYNYL COMPLEXES [(ETA-5-C5R5)M(CO)2]2(MU-C2R) [J].

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[4] REACTION OF THE METAL-SUBSTITUTED VINYLIDENE COMPLEX CP'(CO)2MN[=C=(H)-FP-ASTERISK] WITH EXCESS BULI, GIVING ACYLATED DINUCLEAR BRIDGING ALKENYL COMPLEXES, CP'MNCP-ASTERISK-FE[MU-CH=C(E)-C(=O)-BU] (MU-CO)(CO)2 (E=H, ME) - CONFIRMATION OF THE INTRAMOLECULAR 1,2-H SHIFT MECHANISM PROPOSED FOR THE FLUXIONAL PROCESS OF THE CATIONIC DIIRON MU-ETHYNYL COMPLEXES [((ETA(5)-C5R5)FE(CO)2)2(MU-C-EQUIVALENT-TO-C-H)]BF4 [J].

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[5] REACTION OF THE CATIONIC DIIRON MU-ETA-1-ETA-2-ACETYLIDE COMPLEXES [(FP)2(C=CR)]BF4 (R = H, PH) WITH NAOME [J].

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[6] STRUCTURE AND REACTIVITY OF C2 SPECIES ON POLYMETALLIC SYSTEMS [J].

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BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1995, 68 (02) :420-432

[7] PREPARATION, STRUCTURE, AND DIVERGENT FLUXIONAL BEHAVIOR OF CATIONIC DINUCLEAR IRON ACETYLIDES [FPSTAR2(C=C-H)]BF4, [FPSTAR2(C=C-PH)]BF4 [J].

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ORGANOMETALLICS, 1990, 9 (03) :816-825

[8] INTERACTION OF IRON ETHYNYL AND ETHYNEDIYL COMPLEXES WITH CP2NI2(CO)2 - FORMATION OF TRINUCLEAR AND TETRANUCLEAR ADDUCTS WITH A MULTIPLY BRIDGING C2H LIGAND [J].

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ORGANOMETALLICS, 1992, 11 (10) :3468-3472

[9] PREPARATION, CHARACTERIZATION, AND SEQUENTIAL TRANSFORMATION OF DICARBIDE CLUSTER COMPOUNDS WITH PERMETALLATED ETHYNE, ETHENE, AND ETHANE STRUCTURES [J].

AKITA, M ;

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (19) :7581-7582

[10] INTERACTION OF ETHYNYLIRON (FP-C-EQUIVALENT-TO-C-H AND FP-ASTERISK-C-EQUIVALENT-TO-C-H) AND ETHYNEDIYLDIIRON COMPLEXES (FP-ASTERISK-C-EQUIVALENT-TO-C-FP-ASTERISK) WITH CO2(CO)8 - FORMATION OF A CLUSTER COMPOUND WHICH IS FLUXIONAL VIA A METAL METAL BOND SCISSION AND RECOMBINATION PROCESS [J].

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ORGANOMETALLICS, 1992, 11 (05) :1825-1830

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