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Сидоров, А. А.; Фомина, И. Г.; Talismanov, S. S.; Александров, Г. Г.; Новоторцев, В. М.; Нефедов, С. Е.; Еременко, И. Л.

doi:10.1023/a:1011349727749

Cited by 25 publications

(26 citation statements)

References 4 publications

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“…and Co(1) is 5 -c.n., therefore the binodal cluster can be represented as 3,5M8-1. This motif is also found in other compounds [146][147][148] [152]. Each Co III is a 2-c.n.…”

Section: Cosupporting

confidence: 68%

High-nuclearity cobalt coordination clusters: Synthetic, topological and magnetic aspects

Kostakis

Perlepes

Блатов

et al. 2012

Coordination Chemistry Reviews

205

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A c c e p t e d M a n u s c r i p t Research highlights We analyzed aspects of the synthetic, reactivity, structural and magnetic chemistry of Co CCs  We classified all the polynuclear Cobalt coordination clusters found in CCDC (CCDC 5.32 Nov. 2010) higher than 4.  All the known Co coordination clusters can be searched by cluster topological symbol and nuclearity, compound name, dimensionality and Refcode. Highlights

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“…and Co(1) is 5 -c.n., therefore the binodal cluster can be represented as 3,5M8-1. This motif is also found in other compounds [146][147][148] [152]. Each Co III is a 2-c.n.…”

Section: Cosupporting

confidence: 68%

High-nuclearity cobalt coordination clusters: Synthetic, topological and magnetic aspects

Kostakis

Perlepes

Блатов

et al. 2012

Coordination Chemistry Reviews

205

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“…The weight losses upon decomposition of 3 and in the last step of decomposition of complex 10 (based on the product of composition Ni(OOCCMe 3 ) 2 ) are 70.3±1.0% and 71.7±1.5%, respec tively. Therefore, the quantitative results of thermo gravimetric analysis, the temperature ranges of the de composition steps, and the qualitative agreement between the thermograms for the compounds under consider ation suggest that solid state thermolysis of dinuclear aqua bridged nickel complexes 10-13 at temperatures higher than 270±10 °C produces the cyclic compound [Ni(OOCCMe 3 ) 2 ] 6 .…”

Section: Resultsmentioning

confidence: 75%

“…Among such compounds are pivalate coordination poly mers of simple composition [M(OOCCMe 3 ) 2 ] n (M is a 3d element). Compounds with M = Fe (S = 2), 1,2 Co (S = 3/2), 3,4 or Ni (S = 1) 5, 6 have already found use in the synthesis of carboxylate complexes. How ever, only the structure of [Fe(OOCCMe 3 ) 2 ] n (1) was established by X ray diffraction.…”

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confidence: 99%

High-spin carboxylate polymers [M(OOCCMe3)2]n of group VIII 3d metals

et al. 2006

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A coordination polymer of the general formula [Co(OOCCMe 3 ) 2 ] n (2) was prepared by mild thermolysis of the coordination polymer of variable composi tion [(HOOCCMe 3 ) x Co(OH) n (OOCCMe 3 ) 2-n ] m , the dinuclear cobalt com plex Co 2 (µ H 2 O)(OOCCMe 3 ) 4 (HOOCCMe 3 ) 4 , the tetranuclear cobalt cluster Co 4 (µ 3 OH) 2 (OOCCMe 3 ) 6 (HOEt) 6 , and the hexanuclear cluster [Co 6 (µ 4 O) 2 (µ n OOCCMe 3 ) 10 (C 4 H 8 O) 3 (H 2 O)]•1.5(C 4 H 8 O) (7) in organic solvents. In the crystal, the poly mer has a chain structure. Unlike thermolysis of cobalt pivalates, thermolysis of the dinuclear complex Ni 2 (µ H 2 O)(OOCCMe 3 ) 4 (HOOCCMe 3 ) 4 gave rise to the hexanuclear complex Ni 6 (µ 2 OOCCMe 3 ) 6 (µ 3 OOCCMe 3 ) 6 (3). The magnetic properties of compound 2 are sub stantially different from those of 3. Compound 2 undergoes the magnetic phase transition into the ordered state at T c = 3.4 K (H = 1 Oe), whereas compound 3 exhibits antiferromagnetic properties. Solid state decomposition of polymeric cobalt carboxylate 2 (below 350 °C) af forded the octanuclear cluster Co 8 (µ 4 O) 2 (µ 2 OOCCMe 3 ) 6 (µ 3 OOCCMe 3 ) 6 (9) as the major product, which sublimes without decomposition. Decomposition of 3 gave nickel oxide as the final product. Pivalates 2 and 3 reacted with 2,3 lutidine in acetonitrile at 80 °C to form the isostructural dinuclear complexes (2,3 Me 2 C 5 H 3 N) 2 M 2 (µ OOCCMe 3 ) 4 (M = Co or Ni). The structures of compounds 3 and 7 were established by X ray diffraction. The structure of polymer 2 was determined by powder X ray diffraction analysis.The development of efficient methods for the synthe sis of convenient starting "spin materials" is of importance for the chemical design of molecular magnets with de sired properties and the preparation of precursors for the production of various inorganic materials by thermo chemical methods. Polynuclear (or even polymeric) metal complexes of constant composition with particular struc tures, which are highly reactive toward various organic donors and are readily decomposed at moderate tempera tures (60-450 °C), hold promise as spin materials. It is desirable that the starting complexes be able to generate "magnetic molecules" (for example, in reactions with or ganic donors) or form materials (for example, oxides by mild thermolysis) with desired physical properties. Among such compounds are pivalate coordination poly mers of simple composition [M(OOCCMe 3 ) 2 ] n (M is a 3d element). Compounds with M = Fe (S = 2), 1,2 Co (S = 3/2), 3,4 or Ni (S = 1) 5,6 have already found use in the synthesis of carboxylate complexes. How ever, only the structure of [Fe(OOCCMe 3 ) 2 ] n (1) was established by X ray diffraction. 7 Most of analogous Co II and Ni II compounds, which were prepared from salts of these metals by the exchange reactions with KOOCCMe 3 in water or by melting aqua acetates (M = Co) with pivalic acid, 3,5 have variable composition [(HOOCCMe 3 ) x M(OH) n (OOCCMe 3 ) 2-n ] m (M = Co or Ni). The structures of these compounds are unknown, * Dedicated to...

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“…The reaction of NiCl 2 with excess potassium pivalate (KPiv) in ethanol affords the chain polymeric compound KNi 4 (Piv) 7 (OH) 2 (EtOH) 6 . In the solid compound, the tetranuclear nick el fragments alternate with potassium atoms.…”

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confidence: 99%

“…In the solid compound, the tetranuclear nick el fragments alternate with potassium atoms. The use of KNi 4 (Piv) 7 (OH) 2 (EtOH) 6 in the reac tion with Ni(hfac) 2 (hfac is the hexafluoroacetylacetonate anion) gave the first polynuclear mixed ligand complexes [K 2 Ni 6 (Piv) 7 (hfac) 3 (OH) 4 (HPiv) 2 (Me 2 CO) 2 ]•1.5C 7 H 16 , [Ni 6 (Piv) 4 (hfac) 4 (OH) 4 (Me 2 CO) 4 ],…”

mentioning

confidence: 99%

Polynuclear mixed-ligand NiII complexes containing pivalate and hexafluoroacetylacetonate ligands: a new single-molecule magnet

et al. 2008

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The reaction of NiCl 2 with excess potassium pivalate (KPiv) in ethanol affords the chain polymeric compound KNi 4 (Piv) 7 (OH) 2 (EtOH) 6 . In the solid compound, the tetranuclear nick el fragments alternate with potassium atoms. The use of KNi 4 (Piv) 7 (OH) 2 (EtOH) 6 in the reac tion with Ni(hfac) 2 (hfac is the hexafluoroacetylacetonate anion) gave the first polynuclear mixed ligand complexes [K 2 Ni 6 (Piv) 7 (hfac) 3 (OH) 4 (HPiv) 2 (Me 2 CO) 2 ]•1.5C 7 H 16 , [Ni 6 (Piv) 4 (hfac) 4 (OH) 4 (Me 2 CO) 4 ],[K 2 Ni 8 (Piv) 8 (hfac) 4 (OH) 6 (H 2 O) 2 (Me 2 CO) 6 ], [Ni 8 (Piv) 10 (hfac) 2 (OH) 2 (MeO) 2 (MeOH) 2 (HPiv) 2 ]•C 6 H 14 , and [Ni 16 (Piv) 10 (hfac) 6 (OH) 10 (MeO) 6 (MeOH) 8 (H 2 O) 6 ]•C 6 H 14 containing both Piv and hfac as the anionic ligands. The molecular and crystal structures of all these compounds were established, and their magnetic properties were studied. All solids containing simultaneously Piv and hfac ligands tend to undergo ferromagnetic ordering with decreasing temperature. The solid [Ni 8 (Piv) 10 (hfac) 2 (OH) 2 (MeO) 2 (MeOH) 2 (HPiv) 2 ]•C 6 H 14 undergoes cooperative magnetic order ing below T c (2.5 K).Recently, it has been shown 1-5 that the presence of excess alkali metal pivalates (M I Piv) in the reaction mix ture hinders the formation of polynuclear complexes con taining Cu II and Co II atoms, which are typical of transi tion metal pivalates, and gives rise to unusual polymers containing alternating s and d block atoms.We found that under similar reaction conditions, Ni II forms the KNi 4 (Piv) 7 (OH) 2 (EtOH) 6 complex (1) in the reaction with KPiv. In the solid phase, the polymeric chains of 1 consist of alternating potassium ions and tetranuclear nickel containing fragments. High solubili ty of compound 1 in organic media stimulated us to perform the reaction of 1 with bis(hexafluoroacetyl acetonato)nickel(II) Ni(hfac) 2 with the aim of examining the possibility of preparing higher nuclearity compounds. This approach proved to be useful. In the present study, we report the synthesis, structures, and magnetic pro perties of hexa , octa , and hexadecanuclear Ni II com plexes characterized by the simultaneous presence of both Piv and hfac anions in the ligand shells of polynuclear complexes. Results and DiscussionHeterometallic compounds based on alkali and tran sition metal pivalates, whose stoichiometric composi tion consists mainly of s block atoms, 1-5 are produced at a high M I Piv : M II molar ratio (~5 : 1-10 : 1) in the reac tion mixtures. Nevertheless, the formation of these com pounds is also possible at a lower LiPiv : CoCl 2 or RbPiv : CoCl 2 ratio (2 : 1), as shown 2 in the study aimed at developing a procedure for the synthesis of Li 7 Co 2 (Piv) 11 (HPiv) 2 and Rb 3 Co 2 (Piv) 7 (Thf)(H 2 O).When studying the K I Piv-Ni II system (~2 : 1-5 : 1), we found that the known tetranuclear complex Ni 4 (Piv) 6 (OH) 2 (EtOH) 6 was obtained as the solid phase in the reaction with the use of a 2 : 1 ratio, 6,7 whereas the previously unknown polymer 1 crystallized whe...

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Cited by 25 publications

References 4 publications

High-nuclearity cobalt coordination clusters: Synthetic, topological and magnetic aspects

High-nuclearity cobalt coordination clusters: Synthetic, topological and magnetic aspects

High-spin carboxylate polymers [M(OOCCMe3)2]n of group VIII 3d metals

Polynuclear mixed-ligand NiII complexes containing pivalate and hexafluoroacetylacetonate ligands: a new single-molecule magnet

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