Optically active pentanuclear wing-tip butterfly heterotrimetallic clusters

Губин, С. П.; Galuzina, T.V.; Golovaneva, I. F.; Klyagina, A. P.; Polyakova, L. A.; Belyakova, O. A.; Zubavichus, Ya. V.; Slovokhotov, Yu.L.

doi:10.1016/s0022-328x(97)00490-7

Cited by 12 publications

(7 citation statements)

References 37 publications

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“…12, 19 During the reaction, the oxidation state of the cobalt atom formally changes from 2+ to 0 followed by its carbonylation. An important role of the redox step in these processes is confirmed by the fact that the reac tion does not occur in the [Fe 6 C(CO) 16 ] 2--Co 2 (CO) 8 system containing no oxidizing agent under the same and even more drastic conditions, and the starting iron cluster is recovered. 16 The possibility of carbonylation of the re duced Co atom with iron carbonyls was demonstrated using the reaction of CoCl 2 with Fe(CO) 5 as an example.…”

Section: Resultsmentioning

confidence: 94%

“…In molecule 1a, four disordered M atoms lie in a single plane, and the com pletely ordered Fe(5) and Ru(5) atoms are in trans posi tions with respect to each other. In molecule 1b, the completely ordered Ru (8) and Ru(8a) atoms related by a twofold axis are in the cis arrangement with respect to each other. The crystallographic axis passes through the bridging carbonyl group, the central carbide atom, and the midpoints of the Ru(8)-Ru(8a) and M(7)-M(7a) bonds.…”

Section: Resultsmentioning

confidence: 99%

“…This process generally involves the removal of a vertex from the metal core fol lowed by the addition of another metal at this posi tion. 1,5- 9 The synthetic potential of this method is far from being exhausted. Hence, we continued studies of transmetallation of [Fe 6 C(CO) 16 ] 2-, extended our inves tigation to a wider range of metallating systems, and gave greater attention to the conditions of this complex reac tion accompanied by oxidative degradation of the starting cluster and products of its transmetallation.…”

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Replacement of Fe atoms by Ru in a carbidocarbonyl cluster [Fe6C(CO)16]2−. Structures of reaction products

et al. 2005

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The reaction of the carbidocarbonyl cluster [Fe 6 C(CO) 16 ] 2-with ruthenium(IV) hydroxo chloride Ru(OH)Cl 3 was studied. At 90-100 °C, the reaction gave products of replacement of Fe atoms by Ru in the [Fe 6 C(CO) 16 ] 2-cluster along with degradation products. Treatment of the replacement products with FeCl 3 afforded the [Fe 2.96 Ru 3.04 C(CO) 17 ] compound (1), which was characterized by X ray diffraction analysis. The crystals of cluster 1 are composed of two types of octahedral molecules (1a and 1b) in a ratio of 2 : 1. Molecules 1a are in general positions, and molecules 1b are located on twofold axes. In both molecules, the Fe and Ru atoms are disordered over four of six positions.Heterometallic clusters are important members in a series of transition metal compounds and are of particular interest for the stereochemistry and materials science. 1,2 Heterometallic carbidocarbonyl clusters 1-4 occupy a spe cial place among these promising compounds. More than 90 such clusters containing from one to four different metals (Fe, Co, Ni, Cr, W, Rh, Pd, Pt, Cu, and Ru) 1-4 have been synthesized and characterized.We have developed procedures for the synthesis of such clusters with specified geometry for a wide range of metals. The most promising method for the preparation of such clusters is based on the indirect replacement of vertices in a metal polyhedron. This process generally involves the removal of a vertex from the metal core fol lowed by the addition of another metal at this posi tion. 1,5-9 The synthetic potential of this method is far from being exhausted. Hence, we continued studies of transmetallation of [Fe 6 C(CO) 16 ] 2-, extended our inves tigation to a wider range of metallating systems, and gave greater attention to the conditions of this complex reac tion accompanied by oxidative degradation of the starting cluster and products of its transmetallation.In the present study, we investigated the reaction of the carbidocarbonyl cluster [Fe 6 C(CO) 16 ] 2-with ruthenium(IV) hydroxochloride Ru(OH)Cl 3 . We iso lated products of replacement of Fe by Ru in the [Fe 6 C(CO) 16 ] 2-cluster along with the earlier de scribed 10,11 derivatives of oxidative degradation products, the clusters (µ H)Ru 2 Fe 2 PdC(CO) 12 (η 3 C 10 H 15 ) and Fe 3 RuPd 2 C(CO) 12 (η 3 C 10 H 15 ) 2 . Results and DiscussionTo perform successful replacement of one metal with another, a combination of the following two conditions is required: redox interaction of the metal carbonyl anion with metal chloride and simultaneous carbonylation of the resulting zero valent metal. 12-15Studies in organometallic chemistry showed that bi nary halides of both main group and transition metals are most reactive in transmetallation reactions. 16,17 Earlier, we have studied the reactions of the cluster anions [Fe 6 C(CO) 16 ] 2-and [Fe 5 C(CO) 14 ] 2-with a number of transition metal halides. 12,17,18 It was found that these dianions, like other metal carbonyls, can reduce transi tion metal halides.For example, heating of rhodium trichloride with [...

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Section: Resultsmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

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Replacement of Fe atoms by Ru in a carbidocarbonyl cluster [Fe6C(CO)16]2−. Structures of reaction products

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“…A structural diversity of heterodimetallic and -trimetallic cores was observed for the pentanuclear species containing Au-Fe [296][297][298][299][300][301][302][303][304][305][306][307][308][309], Au-Ru [267,272,[310][311][312][313][314][315][316][317][318][319][320][321][322][323][324][325] and Au-Os [326][327][328][329][330][331][332][333][334][335]. A (Ph 3 P)Au unit can bridge in a m 3 -fashion a face of a tetrahedral heterodimetallic (Fe 2 Ir 2 , Fe 2 Rh 2 , Ru 2 Rh 2 , Ru 3 Rh, Ru 3 Co) core [296,297,310,311,315] [311]…”

Section: The Trimetallic Complex [Net 4 ][(Ph 3 P)aufe(co) 4 W(co) 5 mentioning

confidence: 96%

“…Related clusters in which the Au (PR 3 ) unit bridges in a m 3 -M,C,M 0 fashion a butterfly CM 4 (M ¼ Fe [305,306], Ru [324]) or CFe 3 Co (M 0 ¼ Co [307], Fe [308]) core are also known, for example (Ph 3 P)AuFe 4 (m 5 -C)(CO) 12 (NO) 228 [Au-Fe 2.820(2)/2.866(2) Å] (Figure 4.38a) [306].…”

Section: The Trimetallic Complex [Net 4 ][(Ph 3 P)aufe(co) 4 W(co) 5 mentioning

confidence: 99%