New modes of thiophene coordination and reactivity: structures of Cp*Ir(.eta.2-thiophene), an iridathiabenzene, and Cp*Ir(.eta.4-thiophene.cntdot.BH3)

Chen, Jiabi; Daniels, Lee M.; Angelici, Robert J.

doi:10.1021/ja00157a032

Cited by 155 publications

(94 citation statements)

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“…Several metallathiabenzenes have been prepared by insertion of at ransition metal into the CÀSb ond of at hiophene ring. [156][157][158][159] Three possible resonance structures are given in Figure 3. The involvement of as ulfur lone pair (and,t herefore, the degree of p-delocalization about the metallacycle) is highly dependento nt he electron-deficiencyo ft he metal centre.I n general,e lectron-deficient metallathiabenzenes possess delocalized p-systems, although the delocalisation is far less extensive than in metallabenzenes or benzene.…”

Section: Metallabenzynesmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

142

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Metallaaromatics can be broadly defined as aromatic compounds in which one of the ring atoms is a transition metal. The metallabenzenes are one important class of these compounds that has undergone extensive study recently. Closely related species such as fused-ring metallabenzenes, heterometallabenzenes, π-coordinated metallabenzenes and metallabenzynes have also attracted considerable attention. Although many metallaaromatics can be considered as metalla-analogues of classic organic aromatic compounds, this is not always the case. Recent seminal studies have shown that metallapentalenes and metallapentalynes, which are metalla-analogues of the anti-aromatic compounds pentalene and pentalyne, are in fact aromatic and highly stable. Very unusual spiro-metallaaromatic compounds have also recently been isolated. In this concepts article, key features of all these intriguing metallaaromatic compounds are discussed with reference to the structural, spectroscopic, reactivity and theoretical studies that have been undertaken. These compounds continue to generate much interest, not only because of the contributions they make to fundamental chemical understanding, but also because of the promise of possible practical applications.

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Section: Metallabenzynesmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

142

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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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“…In contrast, the main group heteroatom‐containing metallabenzenes are much less developed. The known examples are limited to metallapyrylium,5 metallathiabenzene,6 metallapyridine,7 and metallapyridiniums 7. 8 To the best of our knowledge, metallasilabenzene ( II , Figure 1), formed by the replacement of a carbon atom with silicon in metallabenzene, has never been synthesized although several corresponding silacyclopentadienyl complexes ( I , Figure 1)9 or a nonaromatic analogue ( III , Figure 1)10 have been reported.…”

Section: Introductionmentioning

confidence: 99%

Unexpected 1,2‐Migration in Metallasilabenzenes: Theoretical Evidence for Reluctance of Silicon to Participate in π Bonding

Huang

Zhu

2014

Chemistry An Asian Journal

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Density functional theory (DFT) calculations were carried out to investigate the 1,2-migration in metallasilabenzenes. The results suggested that the chloride migration of metallabenzenes is unfavorable due to the loss of aromaticity in the nonaromatic analogues. In sharp contrast, such a migration in metallasilabenzenes is favorable due to the reluctance of silicon to participate in π bonding. The migration of hydride and methyl group from the metal center to the silicon atom in metallasilabenzenes is computed to be also feasible. In addition, the π donor ligand and the third row transition metal can stabilize metallasilabenzenes. Thus, such a migration becomes less favorable thermodynamically and kinetically. These findings could be very helpful for synthetic chemists to realize the first metallasilabenzene.

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New modes of thiophene coordination and reactivity: structures of CpIr(.eta.2-thiophene), an iridathiabenzene, and CpIr(.eta.4-thiophene.cntdot.BH3)

Cited by 155 publications

References 0 publications

Recent Advances in Metallaaromatic Chemistry

Recent Advances in Metallaaromatic Chemistry

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

Unexpected 1,2‐Migration in Metallasilabenzenes: Theoretical Evidence for Reluctance of Silicon to Participate in π Bonding

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