Synthesis of an osmafuran from photochemical hydrolysis of OsCl2(CHC(PPh3)C(O)-η2-CHCH2)(PPh3)2

He, Xumin; Liu, Qixuan; Gong, Lei; Lin, Yumei; Wen, Ting Bin

doi:10.1016/j.inoche.2009.12.016

Cited by 9 publications

(3 citation statements)

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“…The origin of the oxygen atom in rhodacycle is H 2 O. , Subsequently, the group of Lo discovered a similar reactivity for ruthenium complexes. − For example, the authors found that treatment of Tp(NHCPh 2 )(PPh 3 )RuCl with PhCCH in the presence of H 2 O gave two ruthenafurans, and the formation of both was proved by deuteration experiments to involve the participation of H 2 O . Xia, Wen, and co-workers also reported H 2 O-involved reactions for the formation of osmafurans starting from the olefin-coordinated osmium complexes during the period from 2009 to 2010. , …”

Section: Synthetic Methodssupporting

confidence: 64%

“…304 Xia, Wen, and co-workers also reported H 2 O-involved reactions for the formation of osmafurans starting from the olefincoordinated osmium complexes during the period from 2009 to 2010. 307,308 Nucleophilic and electrophilic additions into metal vinylidene ketones or esters are other alternative routes for the preparation of metallafurans. Bruce et al used the estersubstituted ruthenium vinylidene complex 267 to react with silver acetylide to synthesize ruthenafuran 270 (Scheme 86).…”

Section: Synthesis Of Heterometallaaromaticsmentioning

confidence: 99%

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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: Synthetic Methodssupporting

confidence: 64%

Section: Synthesis Of Heterometallaaromaticsmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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“…In 2010, Xia and co-workers [48] also found that water can serve as a nucleophile to attack the olefin coordinated complex 105 to give carbonyl osmafuran 106 in chloroform under UV irradiation. If the starting was replaced by complex 107, it could also be converted to osmafuran 108 in 52 % yield for 5 d at room temperature even without UV irradiation (Scheme 25) [49].…”

Section: Oxidation By Air or Tertiary Amine Oxidementioning

confidence: 99%

Metallafurans and their synthetic chemistry

Chen

Xia

2016

Science Bulletin

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cine‐Substitution Reactions of Metallabenzenes: An Experimental and Computational Study

Wang

Zhang

Han

et al. 2013

Chemistry A European J

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Alkali-resistant osmabenzene [(SCN)2(PPh3)2Os{CHC(PPh3)CHCICH}] (2) can undergo nucleophilic aromatic substitution with MeOH or EtOH to give cine-substitution products [(SCN)2(PPh3)2Os{CHC(PPh3)CHCHCR}] (R=OMe (3), OEt(4)) in the presence of strong alkali. However, the reactions of compound 2 with various amines, such as n-butylamine and aniline, afford five-membered ring species, [(SCN)2(PPh3)2Os{CH=C(PPh3)CH=C(CH=NHR')}] (R'=nBu(8), Ph(9)), in addition to the desired cine-substitution products, [(SCN)2(PPh3)2Os{CHC(PPh3)CHCHC(NHR')}] (R'=nBu(6), Ph(7)), under similar reaction conditions. The mechanisms of these reactions have been investigated in detail with the aid of isotopic labeling experiments and density functional theory (DFT) calculations. The results reveal that the cine-substitution reactions occur through nucleophilic addition, dissociation of the leaving group, protonation, and deprotonation steps, which resemble the classical "addition-of-nucleophile, ring-opening, ring-closure" (ANRORC) mechanism. DFT calculations suggest that, in the reaction with MeOH, the formation of a five-membered metallacycle species is both kinetically and thermodynamically less favorable, which is consistent with the experimental results that only the cine-substitution product is observed. For the analogous reaction with n-butylamine, the pathway for the formation of the cine-substitution product is kinetically less favorable than the pathway for the formation of a five-membered ring species, but is much more thermodynamically favorable, again consistent with the experimental conversion of compound 8 into compound 6, which is observed in an in situ NMR experiment with an isolated pure sample of 8.

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Synthesis of an osmafuran from photochemical hydrolysis of OsCl2(CHC(PPh3)C(O)-η2-CHCH2)(PPh3)2

Cited by 9 publications

References 17 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Metallafurans and their synthetic chemistry

cine‐Substitution Reactions of Metallabenzenes: An Experimental and Computational Study

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