Reaction of copper(I) phenoxide with PhNCS: formation and X-ray structure of a novel copper(I) hexameric complex

Narasimhamurthy, N.; Samuelson, Ashoka G.; Manohar, H.

doi:10.1039/c39890001803

Cited by 23 publications

(24 citation statements)

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“…This is surprising since similar adducts have been isolated in the case of CS 2 , PhNCS and MeNCS, in the absence of methanol. This result is also completely different from the reactivity patterns exhibited by aryloxide ligands [3] and hence unique to the hydroxide ligand and CS 2 . The isolated S-capped tetrameric cluster 8 is known in the literature from the reaction of [Cu 2 (dppm) 2 (NO 3 ) 2 ] with Na 2 S [13].…”

Section: Reactions Of the Hydroxo Complexcontrasting

confidence: 55%

“…Attempts to recrystallise 7 from acetonitrile solution led to the formation of crystalline [Cu 2 (dppm) 2 (CH 3 CN) 4 ]-(ClO 4 ) 2 [4] as the major product. The reversible insertion of MeNCS has been documented recently in the case of Cu(I)-aryloxy complexes [3]. Such a ready extrusion of PhNCS was not observed in the case of complex 6.…”

Section: Reactions Of the Hydroxo Complexmentioning

confidence: 94%

“…There was no improvement even after attempts were made to solve the structure from three independent data sets collected from three different crystals. In spite of these limitations, the structural study provides better understanding of the chemistry of heterocumulenes and their reaction with the [Cu 3 (dppm) 3 OH] 2+ cluster (Scheme 2).…”

Section: Reactions Of the Dimermentioning

confidence: 99%

“…Reactions of Cu(I)-aryloxide which has a hard donor coordinated to it reacts with heterocumulenes to give insertion products [3]. These are followed by rearrangements driven by the tendency of Cu(I) to have soft ligands around it [3,4].…”

Section: Introductionmentioning

confidence: 99%

“…Extensive studies done with heterocumulenes indicate the major reaction pathway to be an insertion of the OR group of M-OR fragment into the more polar double bond of Y‚C‚X [2]. This is followed by a rearrangement if necessary to form a M-X or M-Y bond or even a chelated complex with both X and Y bonded to M [3,4]. In the recent past, it has come to light that there could be significant differences in the reactivity of late transition metal alkoxides and aryloxides, especially in their reactions with electrophiles such as SO 2 , CO 2 , and COS [5].…”

Section: Introductionmentioning

confidence: 99%

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Reactions of Cu3(dppm)3(μ3-OH)(ClO4)2 (dppm=bis-(diphenylphosphino) methane) with Soft Heterocumulenes

Sivasankar

Bera

Nethaji

et al. 2004

Journal of Organometallic Chemistry

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Section: Reactions Of the Hydroxo Complexcontrasting

confidence: 55%

Section: Reactions Of the Hydroxo Complexmentioning

confidence: 94%

Section: Reactions Of the Dimermentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Reactions of Cu3(dppm)3(μ3-OH)(ClO4)2 (dppm=bis-(diphenylphosphino) methane) with Soft Heterocumulenes

Sivasankar

Bera

Nethaji

et al. 2004

Journal of Organometallic Chemistry

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Structural and NMR Studies of the Hexameric Copper(I) Complex with N‐n‐butyl‐N′‐ethoxycarbonyl‐thioureate

Boyd

Healy

Hope

et al. 2008

Zeitschrift anorg allge chemie

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The copper sulfide mineral flotation collector, N‐n‐butyl‐N′‐ethoxycarbonyl‐thiourea (H2bectu), and the 1:1 hexameric copper(I) thioureate complex, [Cu(Hbectu)]6, have been characterized by single crystal X‐ray diffraction. H2bectu crystallizes in the triclinic space group $\rm P{\bar 1}$ with a = 5.2754(4), b = 9.0042(7), c = 12.6030(9) Å, α = 80.528(6), β = 90.173(6), γ = 76.472(7)°. An intramolecular N‐H···O hydrogen bond between the thioamide proton and carbonyl oxygen forms a planar six‐membered ring in the central core of the molecule with C=O, C=S and C‐N bond lengths in accord with those reported for other N‐alkyl/aryl‐N′‐acyl‐thiourea compounds. [Cu(Hbectu)]6 crystallizes in the monoclinic space group C2/c with a = 23.269(5), b = 13.243(4), c = 23.037(7) Å, β = 91.81(2)° as discrete hexameric clusters disposed about a crystallographic centre of symmetry with a Cu6S6 core consisting of two Cu3S3 chair‐shaped rings linked by coordination of the deprotonated amide nitrogen atom to a copper atom in the adjacent ring. The six ligands assemble as a paddlewheel structure with the ethoxy and n‐butyl substituents packing in an alternating head to tail arrangement. Temperature dependent solution 1H NMR spectroscopic studies show that the hexameric structure of the complex is maintained in solution.

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Structure and reactivity of copper(I) oligomers

Abraham

Samuelson

Nethaji

1995

Proc. Indian Acad. Sci. (Chem. Sci.)

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The reactivity of oligomeric copper(I) complexes towards test electrophiles and hydrogen have been studied. The complexes exhibit similar reactivity patterns in most cases. Photochemical irradiation of the tetramer 4, led to the isolation of the ligand 8, 2,6-dimethylphenyl-N-phenylthionocarbamate, present in the tetramer. This compound crystallized in the monoclinic system in the P21/n space group with a = I 1'992(5),~, b = 9"886(3) ,~, c = 12"783(6) ,~, fl = 115"91(4) ~ V = 1360"37(4) k 3, z = 4. The comparison of the structure of the ligand with the tetramer shows the differences in the structure brought about by coordination. A comparison of the structures of the tetramer_4 and the bexamer _5 brings out the differences in the nature of bridging sulphide which considerably alters the properties of the complexes. Differences in the reactivity can be understood in terms of the type of the sulphide bridge present in the complexes. Similarities in the reactivity trends are the result of the dissociation of the oligomers in solution. 1H NMR studies reveal that the structures of these complexes in the solution state are different from the solid state and account for the similarities in the reactivity patterns of these complexes.

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Reaction of copper(I) phenoxide with PhNCS: formation and X-ray structure of a novel copper(I) hexameric complex

Cited by 23 publications

References 1 publication

Reactions of Cu3(dppm)3(μ3-OH)(ClO4)2 (dppm=bis-(diphenylphosphino) methane) with Soft Heterocumulenes

Reactions of Cu3(dppm)3(μ3-OH)(ClO4)2 (dppm=bis-(diphenylphosphino) methane) with Soft Heterocumulenes

Structural and NMR Studies of the Hexameric Copper(I) Complex with N‐n‐butyl‐N′‐ethoxycarbonyl‐thioureate

Structure and reactivity of copper(I) oligomers

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