Carbonylchlorido(1-methylsulfanylpenta-1,3-dien-1-yl-5-ylidene)bis(triphenylphosphane)osmium(II)

Johns, Paul M.; Roper, Warren R.; Woodgate, Scott D.; Wright, L. James

doi:10.1107/s1600536809039695

Cited by 8 publications

(6 citation statements)

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“…456 480 could be further replaced by an appropriate anion X − , producing osmabenzenes 479 and 481−483, in which the X and the SMe-substituted carbon are mutually cis (Scheme 152). 456,457 When heated to 80 °C in benzene, 479 isomerized to 484, through position changes between CO and I. Sequential treatment of 484 with AgCF 3 SO 3 and X − resulted in the substitution of I by X again, and 485−487 were isolated (Scheme 152). 456 Ancillary ligand substitution reactions have also been discovered in Roper's iridabenzenes 137 and 139.…”

Section: Reactivities Of Metallabenzenesmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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Since the prediction of the existence of metallabenzenes in 1979, metallaaromatic chemistry has developed rapidly, due to its importance in both experimental and theoretical fields. Now six major types of metallaromatic compounds, metallabenzenes, metallabenzynes, heterometallaaromatics, dianion metalloles, metallapentalenes and metallapentalynes (also termed carbolongs), and spiro metalloles, have been reported and extensively studied. Their parent organic analogues may be aromatic, non-aromatic, or even anti-aromatic. These unique systems not only enrich the large family of aromatics, but they also broaden our understanding and extend the concept of aromaticity. This review provides a comprehensive overview of metallaaromatic chemistry. We have focused on not only the six major classes of metallaaromatics, including the main-group-metal-based metallaaromatics, but also other types, such as metallacyclobutadienes and metallacyclopropenes. The structures, synthetic methods, and reactivities are described, their applications are covered, and the challenges and future prospects of the area are discussed. The criteria commonly used to judge the aromaticity of metallaaromatics are presented.

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Section: Reactivities Of Metallabenzenesmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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“…Since these early reports the study of metallabenzenes has flourished. [39][40][41][42][43][44] The third row transition metalsa re well-represented with examples incorporating osmium, [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] iridium, [62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80] platinum [81][82][83][84] and, most recently,r henium. [85][86][87] Metallabenzenes of one second row transition metal, ruthenium, are also known.…”

Section: Metallabenzenesmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

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145

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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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“…We have represented the structure of 1 with the CF 3 SO 3 − anion coordinated to osmium in the position cis to the SMe-substituted metallabenzene carbon (C1) because of the similarity between the IR and NMR spectral properties of 1 and the closely related osmabenzenes 2a − c . The structure of 2b has been reported previously, and the X-ray crystal structure determination of 2c is discussed below. However, the possibility that the CF 3 SO 3 − anion is present as an uncoordinated counteranion, with either a water molecule or the sulfur atom of the methanethiolate group coordinated to osmium, cannot be ruled out.…”

Section: Resultsmentioning

confidence: 90%

“…The red band was collected, ethanol added, and the dichloromethane removed under reduced pressure. Recrystallization of the bronze material that formed from dichloromethane/ethanol gave pure 3d as bronze-gold crystals (23 J CP = 5.4 Hz) (CO 2 CF 3 not observed). 31 P NMR (CDCl 3 , δ): 3.14.…”

Section: Methodsmentioning

confidence: 99%

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Thermal Rearrangement of Osmabenzenes to Osmium Cyclopentadienyl Complexes

et al. 2010

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The purple osmabenzene complex Os(C5H4{SMe-1})(CF3SO3)(CO)(PPh3)2 (1) is formed in high yield through reaction between Os(C5H4{S-1})(CO)(PPh3)2 and methyl triflate. The neutral blue osmabenzenes Os(C5H4{SMe-1})(cis-X)(CO)(PPh3)2 (X = I (2a), Cl (2b), SCN (2c), CF3CO2 (2d)) are readily obtained through treatment of 1 with the appropriate anion X−. In these complexes the geometry about osmium is approximately octahedral, with the two PPh3 ligands being mutually trans and X being cis to the SMe-substituted carbon of the metallabenzene ring. When solutions of 2a in benzene are heated under reflux, the I and CO ligands interchange positions and the brown isomeric osmabenzene Os(C5H4{SMe-1})(trans-I)(CO)(PPh3)2 (3a) is formed. However, if a solution of either 2a or 3a is heated under reflux in toluene, the metal-bound carbon atoms of the osmabenzene fragment couple and a mixture of the two cyclopentadienyl complexes [Os(η5-C5H4SMe)(CO)(PPh3)2]I (4a) and Os(η5-C5H4SMe)I(CO)(PPh3) (5a) is formed. Heating solutions of 2b−d is not a viable route to the corresponding brown isomers of these compounds, because cyclopentadienyl products are formed directly. In the case of 2b a mixture of the cyclopentadienyl complexes [Os(η5-C5H4SMe)(CO)(PPh3)2]Cl (4b) and Os(η5-C5H4SMe)Cl(CO)(PPh3) (5b) is formed, while in the case of 2c [Os(η5-C5H4SMe)(CO)(PPh3)2]SCN (4c) and Os(η5-C5H4SMe)(SCN)(CO)(PPh3) (5c) are formed. In contrast, [Os(η5-C5H4SMe)(CO)(PPh3)2](CF3CO2) (4d) is the only cyclopentadienyl complex formed on heating solutions of 2d. The brown osmabenzene isomers Os(C5H4{SMe-1})(trans-X)(CO)(PPh3)2 (X = Cl (3b), SCN (3c), CF3CO2 (3d)) are accessible through treatment of 3a with AgCF3SO3, followed by addition of the appropriate anion X−. Heating the brown isomers 3a,b under the same conditions gives the same mixture of cyclopentadienyl complexes that are formed when 2a,b, respectively, are heated. However, 3c,d are resistant to thermal rearrangement and remain unchanged when heated under reflux in toluene. The crystal structures of 2c, 3c, 4d, and 5a have been obtained.

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Carbonylchlorido(1-methylsulfanylpenta-1,3-dien-1-yl-5-ylidene)bis(triphenylphosphane)osmium(II)

Cited by 8 publications

References 10 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Recent Advances in Metallaaromatic Chemistry

Thermal Rearrangement of Osmabenzenes to Osmium Cyclopentadienyl Complexes

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