“…Reactions of transition metal carbonyl complexes with a mixture of elemental sulfur and alkynes have been found to give dithiolene complexes. − Reactions of Cp‘ 2 Fe 2 (CO) 4 with sulfur in the presence of alkynes result in the formation of tetrairon clusters containing both, dithiolene (R 2 C 2 S 2 ) and Cp‘ ligands (eq 17). − When reaction of Fe(CO) 5 with sulfur in the presence of an alkyne was carried out, (R 2 C 2 S 2 ) 4 Fe 4 S 4 was formed, which has been considered to be a cubane type cluster. , …”
Section: B Reactions Of
Bis(cyclopentadienyl)(tetracarbonyl)diiron An...mentioning
confidence: 99%
“…[27][28][29] Reactions of Cp′ 2 Fe 2 (CO) 4 with sulfur in the presence of alkynes result in the formation of tetrairon clusters containing both, dithiolene (R 2 C 2 S 2 ) and Cp′ ligands (eq 17). [30][31][32][33] When reaction of Fe(CO) 5 with sulfur in the presence of an alkyne was carried out, (R 2 C 2 S 2 ) 4 -Fe 4 S 4 was formed, which has been considered to be a cubane type cluster. 34,35 Reaction of {Me 39 Treatment of Fe(BF 4 ) 2 with PEt 3 and H 2 S gives a dicationic cluster [(PEt 3 ) 6 -Fe 6 S 8 ] 2+ (eq 21).…”
“…Reactions of transition metal carbonyl complexes with a mixture of elemental sulfur and alkynes have been found to give dithiolene complexes. − Reactions of Cp‘ 2 Fe 2 (CO) 4 with sulfur in the presence of alkynes result in the formation of tetrairon clusters containing both, dithiolene (R 2 C 2 S 2 ) and Cp‘ ligands (eq 17). − When reaction of Fe(CO) 5 with sulfur in the presence of an alkyne was carried out, (R 2 C 2 S 2 ) 4 Fe 4 S 4 was formed, which has been considered to be a cubane type cluster. , …”
Section: B Reactions Of
Bis(cyclopentadienyl)(tetracarbonyl)diiron An...mentioning
confidence: 99%
“…[27][28][29] Reactions of Cp′ 2 Fe 2 (CO) 4 with sulfur in the presence of alkynes result in the formation of tetrairon clusters containing both, dithiolene (R 2 C 2 S 2 ) and Cp′ ligands (eq 17). [30][31][32][33] When reaction of Fe(CO) 5 with sulfur in the presence of an alkyne was carried out, (R 2 C 2 S 2 ) 4 -Fe 4 S 4 was formed, which has been considered to be a cubane type cluster. 34,35 Reaction of {Me 39 Treatment of Fe(BF 4 ) 2 with PEt 3 and H 2 S gives a dicationic cluster [(PEt 3 ) 6 -Fe 6 S 8 ] 2+ (eq 21).…”
“…The principal difference between the Fe 4 S 5 fragment and the [Fe 4 S 4 ] 2+ core of 8 is insertion of one S(0) atom, nominally into the Fe(4)−S(2) bond of a cubane core (Figure ). Clusters containing the cubanoid Fe 4 S 5 core are well established. − Of the two known forms of this core type, Fe 4 (μ 3 -S) 3 (μ 3 :η 2 η 2 -S 2 ) 17 ( 9a ) and Fe 4 (μ 3 -S) 3 (μ 3 :η 2 η 1 -S 2 ) 18 ( 9b ), the latter connectivity applies to 6 . Each fragment includes two low-spin sites Fe II (1,2) (vide infra) with distorted octahedral FeS 3 C 3 coordination units having bond distances and angles closely comparable with the Fe(1,2) sites of 8 .…”
Reaction of the cubane cluster [Fe 4 S 4 (SEt) 2 (Bu t NC) 6 ] (7) and PhCH 2 SSSCH 2 Ph in benzene solution affords the cluster [Fe 8 S 12 (Bu t NC) 12 ] (6) in 60-74% yield. The structure of this cluster as [6]‚5C 6 H 6 and that of [Fe 4 S 4 (SEt) 2 (Bu t NC) 6 ] (8, closely related to 7) were determined by X-ray diffraction. Cluster 6 contains two cubanoid units Fe 4 S 5 ) Fe 4 (µ 3 -S) 3 (µ 3 :η 2 η 1 -S 2 ) bridged by two µ 2 -S ions and related by an inversion center. Certain features of the structure of 7 as revealed by 8 are retained in 6, including in each cubanoid unit two low-spin distorted octahedral Fe II S 3 (Bu t NC) 3 and two distorted tetrahedral Fe III (µ 3 -S) 3 (µ 2 -S) sites and certain dimensional similarities. The formal insertion of an S(0) atom into a cubane to form a cubanoid unit disrupts one Fe-(µ 3 -S) bond and leads to dimensional changes such as to poise one iron atom in a stereochemistry and position favorable for the formation of an Fe-(µ 2 -S)-Fe bridge. The structures of iron-sulfur polycubanes are summarized; doubly sulfido-bridged double cubanes are unknown. In this family, cluster 6 is the only authenticated bis(µ 2 -S) species and thus bears a distant relationship to the P clusters of nitrogenase. Cluster 6, with four Fe(III) sites in the centrosymmetric array [Fe 2 (µ 2 -S) 2 ](µ 2 -S) 2 , presents an exchange coupling problem not previously encountered in iron-sulfur compounds. A formal treatment of the problem based on two coupling constants for intra-(J) and intercubanoid (J ′) exchange is presented. It is shown that the there is no unique solution for J,J ′. Reasonable values of these parameters based on different assumptions are considered. If a recently determined J value for coupling in a [Fe 2 (µ 2 -S) 2 ] 2+ fragment of a cubane cluster is adopted, J ) 280 cm -1 and J ′ ) 445 cm -1 for 6.
“…In some cases self-assembly methodologies starting from low nuclearity complexes have proven to be a convenient entry to dithiolene-containing clusters, for example, those containing a cubane-type Fe 4 S 4 structure. 12,13 Remarkably, the ability of the dithiolene ligands to coordinate in different fashions yields interesting and unexpected polynuclear complexes with dithiolene-bridged ligands, for example, the dinuclear rhenium (PPh 4 ) 2 [Re 2 (µ-dmit)(dmit) 4 ] (PPh 4 ) tetraphenylphosphonium) compound or several tetranuclear complexes, that is, Au 4 (µ-dmit) 2 (µ-dppm) 2 , and (Me 4 N) 2 {Cu 4 [4,5-(methylsulfanyl) 2 -TTF 3 ]}. [14][15][16] Therefore, the development of rational entries to 1,2-bis(dithiolene) cluster compounds remains a field to be explored.…”
Section: Introductionmentioning
confidence: 99%
“…Since then an enormous interest has been launched in the study of other dithiolene ligands coordinated to less usual systems, including “f-” or “p-block” elements. − In contrast, the use of polynuclear units combined with these ligands has been scarcely studied mainly as a result of the lack of rational synthetic entries to this class of compounds. In some cases self-assembly methodologies starting from low nuclearity complexes have proven to be a convenient entry to dithiolene-containing clusters, for example, those containing a cubane-type Fe 4 S 4 structure. , Remarkably, the ability of the dithiolene ligands to coordinate in different fashions yields interesting and unexpected polynuclear complexes with dithiolene-bridged ligands, for example, the dinuclear rhenium (PPh 4 ) 2 [Re 2 (μ-dmit)(dmit) 4 ] (PPh 4 = tetraphenylphosphonium) compound or several tetranuclear complexes, that is, Au 4 (μ-dmit) 2 (μ-dppm) 2 , and (Me 4 N) 2 {Cu 4 [4,5-(methylsulfanyl) 2 -TTF 3 ]}. − Therefore, the development of rational entries to 1,2-bis(dithiolene) cluster compounds remains a field to be explored.…”
A new series of complexes with the general formula (n-Bu4N)2[M2O2(micro-Q)2(dmit)2] (where M = Mo, W; Q = S, Se; dmit = 1,3-dithiole-2-thione-4,5-dithiolate) have been prepared. Fragmentation of the trinuclear cluster (n-Bu4N)2[Mo3(micro3-S)(micro-S2)3(dmit)3] in the presence of triphenylphosphine (PPh3) gives the dinuclear compound (n-Bu4N)2[Mo2O2(micro-S)2(dmit)2] [(n-Bu4N)2[2]], which is formed via oxidation in air from the intermediate (n-Bu4N)2[Mo3(micro3-S)(micro-S)3(dmit)3] [(n-Bu4N)2[1]] complex. Ligand substitution of the molybdenum sulfur bridged [Mo2O2(micro-S)2(dimethylformamide)6]2+ dimer with the sodium salt of the dmit dithiolate also affords the dianionic compound (n-Bu4N)2[2]. The whole series, (n-Bu4N)2[Mo2O2(micro-Se)2(dmit)2] [(n-Bu4N)2[3]], (n-Bu4N)2[W2O2(micro-S)2(dmit)2] [(n-Bu4N)2[4]], (n-Bu4N)2[W2O2(micro-Se)2(dmit)2] [(n-Bu4N)2[5]], and (n-Bu4N)2[Mo2O2(micro-S)2(dmid)2] [(n-Bu4N)2[6]; dmid = 1,3-dithiole-2-one-4,5-dithiolate], has been synthesized by the excision of the polymeric (Mo3Q7Br4)x phases with PPh3 or 1,2-bis(diphenylphosphanyl)ethane in acetonitrile followed by the dithiolene incorporation and further degradation in air. Direct evidence of the presence of the intermediates with the formula [M3Q4(dmit)3]2- (M = Mo, W; Q = S, Se) has been obtained by electrospray ionization mass spectrometry. The crystal structures of (n-Bu4N)2[1], (PPh4)2[Mo2O2(micro-S)2(dmit)2] [(PPh4)2[2]; PPh4 = tetraphenylphosphonium], (n-Bu4N)2[2], (n-Bu4N)2[4], (PPh4)2[W2O2(micro-Se)2(dmit)2] [(PPh4)2[5]], and (n-Bu4N)2[6] have been determined. A detailed study of the gas-phase behavior for compounds (n-Bu4N)2[2-6] shows an identical fragmentation pathway for the whole family that consists of a partial breaking of the two dithiolene ligands followed by the dissociation of the dinuclear cluster.
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