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Evstaf'ev, V. P.; Kononova, E. A.; Levin, Anat; Trofimova, G. L.; Иванова, О. В.

doi:10.1023/a:1014222928753

Cited by 5 publications

(2 citation statements)

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“…Molecules concentric with a chloride-centered cubic Cu I skeleton surrounded by 12 sulfur atoms in a distorted icosahedral cage are believed to be the most stable species in the series of anion-centered cubic copper clusters. ,,,, This characteristic is further demonstrated in the mixed-valence cluster of Cu I 8 Cu II 6 (Cl)(D-Pen) 12 5− and extended to the selenium-donor ligands. , Unfortunately, the replacement reaction of chloride by hydride is not reversible. Otherwise, this reaction may provide an alternative way to regenerate the dithiophosphate copper species, which are key ingredients of the antioxidants in lubricant oils …”

Section: Resultsmentioning

confidence: 99%

Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral Cu^I₈Cage Inscribed in a S₁₂Icosahedral Framework

et al. 2009

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Reaction of [Cu(CH(3)CN)(4)](PF(6)) and NH(4)[S(2)P(OR)(2)] in a 4:3 ratio in acetone at room temperature produces octanuclear dicationic copper complexes [Cu(8){S(2)P(OR)(2)}(6)](PF(6))(2) (R = (i)Pr, 1; Et, 3) in 81 and 83% yields, respectively. On the other hand, reaction of [Cu(CH(3)CN)(4)](PF(6)), NH(4)[S(2)P(OR)(2)], and NaBH(4) in an 8:6:1 molar ratio in THF for 1 h yields [Cu(4)(H)(mu(3)-Cu)(4){S(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, 2a; Et, 4a) in 87 and 82% yields, respectively. In a similar reaction when NaBD(4) is used instead of NaBH(4), [Cu(4)(D)(mu(3)-Cu)(4){S(2)P(OR)(2)}(6)](PF(6)) (R = (i)Pr, 2b; Et, 4b) are obtained in 83 and 78% yields, respectively. Structural elucidations of 2a and 4a reveal the tetracapped tetrahedral Cu(8) cage with an interstitial hydride. Each of the Cu(I) centers is trigonally coordinated by three S atoms, and each of the six dithiophosphate ligands is connected to a Cu(4) butterfly, where the hinge positions are occupied by two copper atoms situated at the vertex of the central tetrahedron and the wingtips are two capping Cu atoms. The 12 S atoms out of the six ligands constitute an icosahedron around the hydride-centered tetracapped tetrahedral Cu(8) framework. Surprisingly, empty Cu(8) clusters 1 and 3 can abstract hydride (or deuteride) from NaBH(4) (or NaBD(4)) in THF to form 2a and 4a (or 2b and 4b), respectively. Apparently the cubic Cu(8) core, which is known to be formed in the reaction of Cu(I) salt and dichalcogenophosph(in)ate ligands, undergoes a tetrahedral contraction due to the strong Cu...H interactions. Interestingly, the chloride can also be replaced from the chloride-centered Cu(8) complex of [Cu(8)(Cl){S(2)P(OEt)(2)}(6)](PF(6)) by hydride (or deuteride) to form 2a and 4a (or 2b and 4b). However, the hydride- and deuteride-centered compounds 2a,b and 4a,b do not allow the guest exchange.

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Section: Resultsmentioning

confidence: 99%

Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral Cu^I₈Cage Inscribed in a S₁₂Icosahedral Framework

et al. 2009

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“…Thus, the TsD-7 additive [2], which is produced from short-chain alcohols,, including one secondary alcohol, exhibits good anti-oxidizing properties, and provides most heavy oils, including level-DM oils with the required anti-scale properties. A more thermally stable dithiophosphate may be needed to ensure the required level of anti-scale properties of the highest series of motor oils.…”

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confidence: 99%

New dithiophosphate additive for motor oils

Evstaf'ev

Kononova

Levin

et al. 2009

Chem Technol Fuels Oils

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The dithiophosphate additive TsD-13, which combines alkyl and aryl radicals in its own structure, is synthesized. In terms of anti-wear properties, it is not inferior to familiar dithiophosphates, whereupon it provides a high level of anti-scale properties to the oil.In a large portion of modern motor oils, the required level of anti-oxidizing, anti-wear, and anti-corrosion properties is provided primarily by the zinc dialkyl-or diaryl dithiophosphates contained in them. The widespread use of this type of additives for more than 60 years is explained by both the unique combination of anti-oxidizing and lubricating properties, and also their comparatively low production costs.The fitting-out of modern engines with a combustion system for spent gases dictates the need for restriction on the concentration of zinc dithiophosphates in the oil, since the phosphorus compounds that are formed during combustion of lube oil poison the burning catalyst. The requirements for limitation of phosphorus content in motor oils enters as a contradiction with the need to improve the anti-wear and anti-oxidizing (antiscale) properties of the oils.Voluminous research has been conducted in a number countries to replace zinc dithiophosphates with compounds that are more acceptable from the standpoint of environmental protection. Two additives, t h e p r o d u c t i o n o f e a c h o f w h i c h r e q u i r e s e x t e n s i v e o u t l a y s , m u s t b e i n t r o d u c e d t o r e p l a c e t h e dithiophosphate [1]. Complete replacement of dithiophosphates by an additive of the same level of functionalproperties, but which does not contain phosphorus is therefore not expected in the near future. Only the problem of lowering the phosphorus content in modern motor oils to 0.08-0.05% is the problem; this will provide for sufficient longevity of the burning catalysts.As we know, dithiophosphates exhibit a different level of functional properties, depending on the reagents selected (alcohols, alkylphenols), and the procedure used for their production. Dialkyl dithiophosphates produced from short-chain, especially secondary, alcohols possess the best anti-oxidizing and anti-wear properties.Thus, the TsD-7 additive [2], which is produced from short-chain alcohols,, including one secondary alcohol, exhibits good anti-oxidizing properties, and provides most heavy oils, including level-DM oils with the required anti-scale properties. A more thermally stable dithiophosphate may be needed to ensure the required level of anti-scale properties of the highest series of motor oils. 235Leading foreign companies produce various dithiophosphates. In addition to the TsD-7 additive, the dithiophosphates DF-11, DFB, and A-22 are produced in Russia from primary alcohols, as well as the diaryl dithiophosphate VNII NP-354. The technology adopted for production of the latter does not ensure its sufficiently high pH, and an additive is obtained with a lower thermal stability than can be achieved with zinc diaryl dithiophosphates.To ensure simultaneously good a...

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Syntheses and structural characterization of new trans-bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato] nickel(II), the pyridine derivative thereof, and bis-{bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato]cobalt(II)} complexes

Sağlam

Dal

Mougang-Soumé

et al. 2020

Journal of Molecular Structure

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Cited by 5 publications

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Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral Cu^I₈Cage Inscribed in a S₁₂Icosahedral Framework

Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral Cu^I₈Cage Inscribed in a S₁₂Icosahedral Framework

New dithiophosphate additive for motor oils

Syntheses and structural characterization of new trans-bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato] nickel(II), the pyridine derivative thereof, and bis-{bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato]cobalt(II)} complexes

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Cited by 5 publications

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Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral CuI8Cage Inscribed in a S12Icosahedral Framework

Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral CuI8Cage Inscribed in a S12Icosahedral Framework

New dithiophosphate additive for motor oils

Syntheses and structural characterization of new trans-bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato] nickel(II), the pyridine derivative thereof, and bis-{bis-[n-butyl-(p-methoxyphenyl) dithiophosphinato]cobalt(II)} complexes

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Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral Cu^I₈Cage Inscribed in a S₁₂Icosahedral Framework

Facile Entrapment of a Hydride inside the Tetracapped Tetrahedral Cu^I₈Cage Inscribed in a S₁₂Icosahedral Framework