Transformations of 3,3-dimethylthietane in triosmium cluster complexes

Adams, Richard D.; Belinski, Judy A.; Pompeo, Michael P.

doi:10.1021/om00042a015

Cited by 29 publications

(19 citation statements)

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“…A similar observation was made for the DMT ligand in 7 . This contrasts with other structural studies of thietane ligands where slight puckering of the thietane rings has been observed . The selenium atom has a pyramidal geometry, and the 1 H NMR spectrum of 1 shows two singlets for the methyl resonances (δ 1.41 (s, 3H), 1.22 (s, 3H)) and an AB quartet for the methylene groups (3.58 (d, 2H, 2 J H-H = 9.4 Hz) and 3.20 (d, 2H, 2 J H- H = 9.7 Hz)) at room temperature, as expected.…”

Section: Resultscontrasting

confidence: 77%

A New Route to Polyselenoether Macrocycles. Catalytic Macrocyclization of 3,3-Dimethylselenetane by Re₂(CO)₉SeCH₂CMe₂CH₂

1997

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was cyclooligomerized catalytically at 115 °C by the Three new polyselenoether macrocycles, 3,3,7,7-tetramethyl-1,5-diselenacyclooctane (2; Me48Se2), 3,3,7,7,11,11-hexamethyl-1,5,9-triselenacyclododecane (3; Me612Se3), and 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetraselenacyclohexadecane (4; Me816Se4), along with a polymer were obtained. Two complexes of 3, Re2(CO)9(Me612Se3) (5) and Cu4I4(μ-Me612Se3)2 (6), were obtained from the reactions with Re2(CO)9(NCMe) and CuI, respectively. All three macrocycles and the complexes 1, 5, and 6 were characterized crystallographically. In all cases the gem-dimethyl groups of the macrocycles are directed toward the exterior of the rings. Interestingly, some methylene groups are directed toward the interior of the ring. Compound 5 contains an η1-Me612Se3 ligand, while compound 6 contains bridging η2-Me612Se3 ligands that link Cu4I4 clusters into a three-dimensional network in the solid state.

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Section: Resultscontrasting

confidence: 77%

A New Route to Polyselenoether Macrocycles. Catalytic Macrocyclization of 3,3-Dimethylselenetane by Re₂(CO)₉SeCH₂CMe₂CH₂

1997

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“…The identity of the anionic, paramagnetic cluster 8 was established unambiguously by preparing it from the one-electron reduction of cubane 2 and structurally characterizing the anion (62). Adams et al have previously observed homolytic C-S bond scission in the reactions of thiols and thietanes with OS3 clusters (45,47,67). In these reactions, multi-point bonding of the thiolate to the cluster is also observed, so that the mechanism of C-S bond activation proposed here applies to the OS3 cluster-mediated reactions as well.…”

Section: Desulfurization Of Thiolate Anions Ars"supporting

confidence: 51%

Hydrodesulfurization Catalysts and Catalyst Models Based on Mo—Co—S Clusters and Exfoliated MoS₂

Curtis

1996

ACS Symposium Series

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“…A different but related example was found in [Os,(CO),(p-SCH,-CMe2CH,)(p-Cl)]-. 34 The S(l) S(2) distance [3.26(2) A] is slightly larger than that in 3 [3.166(8) A]. On the other hand, the Os(3)-N(4) distance [2.19(4) A] is shorter than that in 5 [2.24 (1) A].…”

Section: Resultsmentioning

confidence: 99%

Synthesis, structural characterization and thermal reactivities of osmium carbonyl clusters containing 4,6-dimethylpyrimidine-2-thione

Au¹,

Cheung²,

Wong³

1995

J. Chem. Soc., Dalton Trans.

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The reaction of the labilized cluster [Os,(CO),,( MeCN),] and bis(4.6-dimethylpyrimidin-2-yl) disulfide affords two major products [O~,(CO),~(p-drnpymt),] 1 (36%) and [O~~(CO),,(p-SH)(p-dmpymt)] 2). Cluster 2 is formed from C-S bond cleavage of one of the dmpymt ligands at ambient conditions. Thermolysis of cluster 1 in n-heptane (98 "C) for 1 h produces an isomeric cluster of 1, [Os,(CO),,(p-dmpymt),] 3 (62%). which contains two dmpymt ligands co-ordinated across the same non-bonding Os...Os edge. Thermolysis of cluster 3 in nheptane for 2 h affords the cluster [Os,(CO),(p-dmpymt) (p3-qz-dmpymt)] 4 as the major product (42%) in addition t o a minor product [Os,(CO),(p-q2-dmpymt)(p3-qz-dmpymt)] 5 (9%). Cluster 4contains two dmpymt moieties co-ordinating in p and p3-q2 modes respectively. Cluster 5 has two dmpymt moieties bonding in the p3-q2 and p-q2 modes respectively. Further thermolysis of cluster 4 in n-octane (125°C) leads to a much higher yield of cluster 5 (60%) at the expense of cluster 4. Chemical activation of cluster 1 using Me,NO in CH,CI, at -78°C also produces clusters 4 and 5 in 20 and 15% yield respectively. A new, orange product (31%) is also formed but remains uncharacterized. When cluster 4 is allowed to stand under ambient conditions over a period of ten days, it isomerizes to the cluster [Os,(CO),(p-dmpymt) (p-q2-dmpymt)] 6 in almost quantitative yield (87%). Cluster 6 contains one dmpymt ligand co-ordinating in the p-q2 five-electron donating mode.Cluster 5 undergoes carbonylation to form cluster 4 (62%) under a CO atmosphere in CH,CI, while cluster 4 also changes back to cluster 3 (47%) in refluxing n-hexane (69 "C) under a CO atmosphere. Formation of clusters 3-5 is thus reversible. Mechanisms for the formation of 3, 4 and 6 have also been proposed. All the clusters 1-6 isolated have been fully characterized by conventional spectroscopic methods as well as single-crystal X-ray analyses.

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Transformations of 3,3-dimethylthietane in triosmium cluster complexes

Cited by 29 publications

References 0 publications

A New Route to Polyselenoether Macrocycles. Catalytic Macrocyclization of 3,3-Dimethylselenetane by Re₂(CO)₉SeCH₂CMe₂CH₂

A New Route to Polyselenoether Macrocycles. Catalytic Macrocyclization of 3,3-Dimethylselenetane by Re₂(CO)₉SeCH₂CMe₂CH₂

Hydrodesulfurization Catalysts and Catalyst Models Based on Mo—Co—S Clusters and Exfoliated MoS₂

Synthesis, structural characterization and thermal reactivities of osmium carbonyl clusters containing 4,6-dimethylpyrimidine-2-thione

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Transformations of 3,3-dimethylthietane in triosmium cluster complexes

Cited by 29 publications

References 0 publications

A New Route to Polyselenoether Macrocycles. Catalytic Macrocyclization of 3,3-Dimethylselenetane by Re2(CO)9SeCH2CMe2CH2

A New Route to Polyselenoether Macrocycles. Catalytic Macrocyclization of 3,3-Dimethylselenetane by Re2(CO)9SeCH2CMe2CH2

Hydrodesulfurization Catalysts and Catalyst Models Based on Mo—Co—S Clusters and Exfoliated MoS2

Synthesis, structural characterization and thermal reactivities of osmium carbonyl clusters containing 4,6-dimethylpyrimidine-2-thione

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Product

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A New Route to Polyselenoether Macrocycles. Catalytic Macrocyclization of 3,3-Dimethylselenetane by Re₂(CO)₉SeCH₂CMe₂CH₂

A New Route to Polyselenoether Macrocycles. Catalytic Macrocyclization of 3,3-Dimethylselenetane by Re₂(CO)₉SeCH₂CMe₂CH₂

Hydrodesulfurization Catalysts and Catalyst Models Based on Mo—Co—S Clusters and Exfoliated MoS₂