A model for thiophene chemisorption:  a stabilized, .eta.1S-thiophene complex and its relationship to .eta.5-coordination

Draganjac, M.; Ruffing, Charles J.; Rauchfuss, Thomas B.

doi:10.1021/om00129a045

Cited by 77 publications

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“…Conventionally, thiophene is considered to coordinate poorly to transition metals although there are several recent examples in which M-S(thiophene) distances have been found that are roughly equal to the sum of the covalent radii of divalent sulfur and the metal involved (7)(8)(9)(10)(11)(12)(13)(14)(15). In addition, there are compounds in which weaker interactions occur that can be detected spectroscopically and for which the M-S distance is much longer (16).…”

Section: %mentioning

confidence: 99%

X-ray structural and nuclear magnetic resonance study of open chain and macrocyclic thioether complexes

Lucas¹,

Liu²,

Newlands³

et al. 1990

Can. J. Chem.

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. Can. J. Chem. 68, 1357 (1990). Preparations of the thiophenophane and open chain thioether complexes MX2.BBTE (M = Pd; X = C1, I) (M = Pt; X = C1) (BBTE = 1,2-bis(benzy1thio)ethane) and MX2.L (M = Pd; X = C1, Br, I, SCN) (M = Pt; X = C1) (L = 2,5,8-trithia[9](2,5)thiophenophane) are described. The molecular structure of PdBr2.L which contains a weak thiophene-sulfur-topalladium interaction has been determined: space group P2]/n, a = 8.3569(3), b = 16.3254(15), c = 11.1462(3) A, P = 92.833(4)", Z = 4, Rf = 0.060, R, = 0.058. The electronic, low frequency ir, and I3C nrnr spectra are described. Variable temperature 'H nmr spectra are discussed and it is concluded that the open chain complexes undergo rapid conformational exchange at room temperature but are configurationally rigid unless the temperature is increased. In contrast, the macrocyclic complexes undergo very limited conformational and no configurational exchange up to theu decomposition temperatures. They are also nonfluxional in the same temperature range. Chemical exchange of acidic ligand hydrogens and a metal-ligand dissociative equilibrium were also detected when X = SCN.Key words: thiophene, thioether, macrocyclic metal complexes. On discute des spectres rmn du 'H a tempkrature variable et on en conclut que, a la temptrature ambiante, les complexes avec des chaines ouvertes subissent des tchanges conformationnels rapides; toutefois, ils sont rigides d'un point de vue configurationnel, i moins que l'on augmente la temptrature. Par ailleurs, lorsqu'on soumet les complexes avec des macrocycles B des temptratures allant jusqu'i leurs temptratures de dtcomposition, ils ne subissent que des tchanges conformationnels et configurationnels trts limitts. Dans le cas oil X = SCN, on a aussi dttectt un tchange chimique impliquant les hydrogtnes acides agissant comme ligands ainsi qu'un tquilibre mttal ligand impliquant une dissociation.

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Section: %mentioning

confidence: 99%

X-ray structural and nuclear magnetic resonance study of open chain and macrocyclic thioether complexes

Lucas¹,

Liu²,

Newlands³

et al. 1990

Can. J. Chem.

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“…In fact, there exist several reasonable bonding modes in metal thiophenes (see Fig. 1b ), including sulfur coordination ( κ 1 -S) 21 – 23 and a variety of π adducts ( η 2 , η 4 , or η 5 ) 24 – 27 . A direct analogy between arene and thiophene binding modes is, therefore potentially problematic as has been noted previously 23 , 28 .…”

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Identifying the missing link in catalyst transfer polymerization

Patrick

Kennepohl

2018

Nat Commun

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Nickel-catalyzed catalyst transfer polycondensation (CTP) of thiophenes is an efficient strategy for the controlled synthesis of polythiophenes. However, a detailed view of its reaction mechanism has remained elusive with unresolved questions regarding the geometry and bonding of critical Ni(0) thiophene intermediates. Herein, we provide experimental and computational evidence of structurally characterized square planar η2-Ni(0)–thiophene species and their relevance to the mechanism of CTP. These results confirm the viability of C,C-η2 bound intermediates in CTP of thiophenes, providing an electronic rationale for the stability of such species, and thus that such processes can proceed as living polymerizations. We further show that C,S-κ2 species may also be relevant in nickel-catalyzed CTP of thiophenes, providing new avenues for exploitation and optimization.

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“…Studies of thiophenes on surfaces [5,[9][10][11][12] and of homogeneous transition-metal-fhiophenic complexes [13] have been focused on binding geometry and subsequent reactivity. Several different binding geometries have been characterized for homogeneous transition-metal-thiophene complexes including 711-S bound [14,IS], 712-bound [16], 714-bound [17][18][19], and 71s-bound [17,[20][21][22], 1-4.…”

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Transition-metal mediated heteroatom removal by reactions of FeL⁺ [L=O, C₄H₆, c-C₅H₆, c-C₅H₅, C₆H₆, C₅H₄(=CH₂)] with furan, thiophene, and pyrrole in the gas phase

Bakhtiar

Jacobson

1996

J. Am. Soc. Mass Spectrom.

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Reactions of Fe(+) and FeL(+) [L=O, C4H6, c-C5H6, C5H5, C6H6, C5H4(=CH2)] with thiophene, furan, and pyrrole in the gas phase by using Fourier transform mass spectrometry are described. Fe(+), Fe(C5H5)(+), and FeC6H 6 (+) yield exclusive rapid adduct formation with thiophene, furan, and pyrrole. In addition, the iron-diene complexes [FeC4H 6 (+) and Fe(c-C5H6)(+)], as well as FeC5H4(=CH2)(+) and FeO(+), are quite reactive. The most intriguing reaction is the predominant direct extrusion of CO from furan by FeC4H6 (+), Fe(c-C5H6)(+), and FeC5H4(=CH2)(+). In addition, FeC4H 6 (+) and Fe(c-C5H6)(+) cause minor amounts of HCN extrusion from pyrrole. Mechanisms are presented for these CO and HCN extrusion reactions. The absence of CS elimination from thiophene may be due to the higher energy requirements than those for CO extrusion from furan or HCN extrusion from pyrrole. The dominant reaction channel for reaction of Fe(c-C5H6)(+) with pyrrole and thiophene is hydrogen-atom displacement, which implies D(O)(Fa(N5H5)(+)-C4H4X)>D(O)(Fe(C5H5)(+)-H)=46±5 kcal mol(-1). D(O)(Fe(+)-C4H4S) and D(O)(Fe(+)-C4H5N)=D(O)(Fe(+)-C4H6)=48±5 kcal mol(-1). Finally, 55±5 kcal mol(-1)=D(O)(Fe(+)-C6H6)>D(O)(Fe(+)-C4H4O)>D(O)(Fe(+)-C2H4)=39.9±1.4 kcal mol(-1). FeO(+) reacts rapidly with thiophene, furan, and pyrrole to yield initial loss of CO followed by additional neutral losses. D(O)(Fe(+)-CS)>D(O)(Fe(+)-C4H4S)≈48±5 kcal mol(-1) and D(O)(Fe(+)-C4H5N)≈48±5 kcal mol(-1)>D(O)(Fe(+)-HCN)>D(O)(Fe(+)-C2H4)=39.9±1.4 kcal mil(-1).

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A model for thiophene chemisorption: a stabilized, .eta.1S-thiophene complex and its relationship to .eta.5-coordination

Abstract: for the opportunity offered to R.W. in 1983 to discuss deeply the specific experimental and theoretical facets of 119Sn NMR.

Cited by 77 publications

References 0 publications

X-ray structural and nuclear magnetic resonance study of open chain and macrocyclic thioether complexes

X-ray structural and nuclear magnetic resonance study of open chain and macrocyclic thioether complexes

Identifying the missing link in catalyst transfer polymerization

Transition-metal mediated heteroatom removal by reactions of FeL⁺ [L=O, C₄H₆, c-C₅H₆, c-C₅H₅, C₆H₆, C₅H₄(=CH₂)] with furan, thiophene, and pyrrole in the gas phase

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A model for thiophene chemisorption: a stabilized, .eta.1S-thiophene complex and its relationship to .eta.5-coordination

Abstract: for the opportunity offered to R.W. in 1983 to discuss deeply the specific experimental and theoretical facets of 119Sn NMR.

Cited by 77 publications

References 0 publications

X-ray structural and nuclear magnetic resonance study of open chain and macrocyclic thioether complexes

X-ray structural and nuclear magnetic resonance study of open chain and macrocyclic thioether complexes

Identifying the missing link in catalyst transfer polymerization

Transition-metal mediated heteroatom removal by reactions of FeL+ [L=O, C4H6, c-C5H6, c-C5H5, C6H6, C5H4(=CH2)] with furan, thiophene, and pyrrole in the gas phase

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Transition-metal mediated heteroatom removal by reactions of FeL⁺ [L=O, C₄H₆, c-C₅H₆, c-C₅H₅, C₆H₆, C₅H₄(=CH₂)] with furan, thiophene, and pyrrole in the gas phase