Selenium-capped trimolybdenum and tritungsten carbonyl clusters [Se2M3(CO)10]2− (M=Mo, W)

Hsu, Miao Hsing; Miu, Chia Yeh; Lin, Yi Chun; Shieh, Minghuey

doi:10.1016/j.jorganchem.2005.10.039

Cited by 15 publications

(5 citation statements)

References 35 publications

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“…The oxygen transfer reaction of the heterometallic carbonyl cluster (μ3-S)FeCo2(CO)9 with bis(pmethoxyphenyl)telluroxide (BMPTO) gives bis(pmethoxyphenyl)telluride (BMPT) coordinated metal cluster products (μ3-S)FeCo2(CO)8(BMPT) and (μ3-S) FeCo2(CO)7(BMPT)2 , which react further with PPh3 to afford Ph3P-substituted derivatives (μ3-S)FeCo2(CO)8(PPh3) and (μ3-S)FeCo2(CO)7(PPh3)2, respectively [201]. [204].…”

Section: Heteronuclear Clustersmentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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KEYWORDSThe special interest attached to the chemistry of metal carbonyls arises from several causes. While quite distinct from the metal carbonyls in the organometallic compounds, they differ in physical properties (e.g., their volatility) from all other compounds of the transition metals. Chemically, they constitute a group of compounds in which the formal valency of the metal atoms is zero, and in this respect (apart, perhaps, from the ammoniates of the alkali metals) they are comparable only with the recently discovered compounds. As a class, the carbonyls are reactive compounds, and a number of new types of inorganic compounds have been discovered. In the concepts for new products, performance, product safety, and product economy criteria are equally important. They are taken into account already when the raw material base for a new industrial product development is defined. Since the discovery of nickel carbonyl by Mond and Langer in 1888, the carbonyls of the iron group and of chromium, molybdenum and tungsten have found important technical applications, e.g., in the Mond nickel process, and for the preparation of the metals in a state of subdivision and of purity suitable for powder metallurgy, for catalysts, etc. The reaction mechanism of the processes developed for producing the carbonyls technically has only recently received its interpretations. Within the space of review it is necessary to limit discussion to a few topics. Particular stress has accordingly laid upon (a) the chemical bonding in metal carbonyls, (b) importance of IR and NMR spectroscopy in characterization of metal carbonyls, (c) substitution reactions of G-VIb metal carbonyls, (d) kinetics and mechanism of substitution reactions in metal carbonyls, (e) substituted complexes of G-VIb metal carbonyl, (f) chelate complexes of G-VIb metal carbonyls, (g) uses of G-VIb metal carbonyl complexes and (h) studies done on G-VIb metal carbonyls.

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Section: Heteronuclear Clustersmentioning

confidence: 99%

The chemistry of group-VIb metal carbonyls

Kaushik¹,

Singh²,

Kumar³

2012

Eur. J. Chem.

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“…This reaction proceeded smoothly, producing [Et 4 N] 2 [ 1 ] as deep brown air-sensitive crystals in a moderate yield. Like the reactions of Cr(CO) 6 with main group oxides in basic solutions, 6f-g,− the reactive species for this reaction were proposed to be [HCr(CO) 5 ] - /[Cr(CO) 5 ] 2- , which could react with Pb 2+ ions in KOH/MeOH to give complex 1 . An X-ray analysis shows that dianion 1 possesses two Pb{Cr(CO) 5 } 2 units bridged by two hydroxo groups.…”

Section: Resultsmentioning

confidence: 99%

“…As part of our studies to probe the coupling effects of main group elements and transition metals, we have been interested in developing rational routes to main group-containing transition metal carbonyl complexes, in attempts to study their structural versatility and properties. − In the chromium-related system, group 15-hydrido trichromium complexes of the type [HE{Cr(CO) 5 } 3 ] 2- (E = As, Sb) 7 and the dichalcogen-capped trichromium clusters [E 2 Cr 3 (CO) 10 ] 2- (E = Se, Te) 8 have been produced from reactions of main group oxides with Cr(CO) 6 under appropriate conditions. These studies demonstrate that the remarkable difference in reactivity between these two classes is closely related to the role of main group elements because of their differing sizes and electronic demands.…”

Section: Introductionmentioning

confidence: 99%

Carbon Dioxide Fixation by an Unprecedented Hydroxo Lead−Chromium Carbonyl Complex: Synthesis, Reactivity, and Theoretical Calculations

et al. 2006

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The novel hydroxo-bridged dimeric lead-chromium carbonyl complex [Et4N]2[{PbCr2(CO)10}2(mu-OH)2] ([Et4N]2[1]) was synthesized from the reaction of PbCl2 and Cr(CO)6 followed by metathesis with [Et4N]Br in a KOH/MeOH solution. The X-ray crystallographic structure shows that dianion 1 consists of two Pb{Cr(CO)5}2 units bridged by two hydroxo fragments in which the Pb atoms are further coordinated with two Cr(CO)5 groups, resulting in a distorted tetrahedral geometry. A CO2 molecule can insert itself into dianion 1 to form two new carbonate complexes, [Et(4)N]2[{PbCr2(CO)10}(CO3)] ([Et4N]2[2]) and [Et4N]2[{PbCr2(CO)10}2(CO3)] ([Et4N]2[3]), depending on the reaction conditions. In addition, complex 2 can be transformed into 3 in CH2Cl2 solution at an elevated temperature. While the carbonate group in dianion 2 is bonded to one Pb atom, which is coordinated with two Cr(CO)5 fragments, the carbonate group in 3 bridges the two Pb centers in a mu-1kappa2OO':2kappa2OO' fashion in which each Pb atom is further bonded to two Cr(CO)5 moieties. Complexes 2 and 3 can be converted back the hydroxo complex 1 under appropriate conditions. All three unprecedented lead-chromium compounds, 1-3, were fully characterized by spectroscopic methods and single-crystal X-ray diffraction analyses. The nature and formation of complexes 1-3 were also examined by molecular orbital calculations using the B3LYP method of the density functional theory.

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“…3 A simple and systematic synthetic route to a series of selenium-capped trimetallic carbonyl clusters has been described. 4 Reaction of Cu(I) acetate with the selenoferrocene reagent Fe(C 5 H 4 SeSiMe 3 ) 2 [Fc(SeSiMe 3 ) 2 ] in the presence of Se(SiMe 3 ) 2 yields the copper(I) selenide cluster Cu 20 Se 6 (FcSe 2 ) 4 (P n Pr 3 ) 10 . Subsequent treatment with Ph 2 P(CH 2 ) 3 SH yields the larger cluster Cu 36 Se 12 (FcSe 2 ) 6 (P n Pr 3 ) 10 -(Ph 2 P(CH 2 ) 3 SH) 2 which offers surface thiol groups on a Cu 2 Se core.…”

Section: Highlights 1 Binary Main Group and Transition Metal Chalcoge...mentioning

confidence: 99%

“…43 Reports of extended TTFs, in which the conjugated core between the two dithiole rings has been extended, include the incorporation of extra double bond(s), 44 triple bond(s), 45 para-quinoid spacer unit(s), 46 a two-way or three-way junction separating dithiole rings using a benzene ring, 47 or combinations of the above. 48 Ouahab et al report the opening of the central CQC bond in a TTF derivative by Cu 2+ salts 49 to form a 1,4,6,9-tetrathia-10-ketospiro [4,5]decane.…”

Section: Tetrathiafulvalenes and Related Derivativesmentioning

confidence: 99%