Formation of Derivative Carbyne Complexes from Tp‘(CO)<sub>2</sub>M⋮CCH<sub>3</sub> (M = Mo, W)

Woodworth, Brian E.; Frohnapfel, David S.; White, Peter S.; Templeton, Joseph L.

doi:10.1021/om9708992

Cited by 37 publications

(31 citation statements)

References 30 publications

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“…Another example for the synthesis of metallafurans through rearrangement is shown in Scheme . The Tp Me2 -based tungsten complex 280 was converted to the seven-coordinate complex 281 in solution, via β-H migration into the α-position …”

Section: Synthetic Methodsmentioning

confidence: 61%

“…The Tp Me2 -based tungsten complex 280 was converted to the seven-coordinate complex 281 in solution, via β-H migration into the αposition. 314 Some other methods, such as isomerization of metallacyclopropene complexes, 315 reaction of tungsten complexes WCl 2 (NAr)(PX 3 ) 3 with ketalcyclopropene, 316 ether bond cleavage in oxygen-containing five-membered metallacycles, 317 and multiple CX cleavage of CF 2 CFCl, 318 have also been developed.…”

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 Methodsmentioning

confidence: 61%

Section: Synthesis Of Heterometallaaromaticsmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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“…Syntheses of the monomeric (1 and 6) [59][60][61] and dimeric (2-5, 7-10) 36,37 carbyne complexes were accomplished using literature routes. Electrochemical data were collected using a Princeton Applied Research 273A potentiostat.…”

Section: Methodsmentioning

confidence: 99%

Variable Electronic Coupling through Hydrocarbon Spacers Bridging Metal−Carbon Triple Bonds

et al. 1998

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The electrochemical behavior of a series of bis-carbyne complexes, Tp‘(CO)2M⋮(C m H n )⋮M(CO)2Tp‘ (Tp‘ = hydridotris(3,5-dimethyl-1-pyrazolyl)borate; M = Mo, W; m = 3, n = 2; m = 4, n = 0, 2, 4), has been studied. These complexes exhibit two oxidation waves between 0 and 0.5 V (vs ferrocene). The difference in E 1/2 for the two oxidation waves is a function of the hydrocarbon spacer with the ⋮C−C⋮C−C⋮ spacers (m = 4, n = 0) exhibiting considerably larger ΔE 1/2 values than the corresponding ⋮C−CHCH−C⋮ spacers (m = 4, n = 2), which were in turn more strongly coupled than the saturated analogues (m = 4, n = 4). While the trend in electronic coupling was quantitatively as expected for the degree of unsaturation in the bridge, the absolute magnitude of the coupling as indicated by the comproportionation constants (K c = 100−104) was much smaller than that in isologous dimers where the bridge is connected to the metal centers via single bonds (K c = 108−1012). A qualitative model based on relevant orbital occupancy as a function of metal oxidation state has been developed to account for the experimental results.

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“…We have established that the vinylidene anion, [Tp‘(CO) 2 MCCH 2 ] - (M = Mo, W), reacts with a variety of electrophiles. 2h, It is also known that metal halides are susceptible to nucleophilic attack, as observed in the reaction of [W]−I with LiMe 2 Cu to form [W]−CH 3 ([W] = Tp‘(CO)(RC⋮CR)W]) . This work merges these two complementary reagents: the vinylidene anion(s) [Tp‘(CO) 2 MCCH 2 ] - reacts with Tp(CO)(I)W(PhC⋮CPh) to form a bridging ligand with a two-carbon framework.…”

Section: Introductionmentioning

confidence: 88%

Deprotonation and Oxidation of the W⋮CCH₂−W Bridge To Form a C₂-Biscarbyne W⋮C−C⋮W Bridge

1998

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Reaction of the anionic vinylidene complex K[Tp′(CO) 2 MdCdCH 2 ] (M ) Mo, W; Tp′ ) hydridotris-(3,5-dimethylpyrazolyl)borate) with Tp(CO)(PhCtCPh)W-I (Tp ) hydridotris(pyrazolyl)borate) yields Tp′-(CO) 2 MCCH 2 -W(CO)(PhCtCPh)Tp (M ) Mo, 4; W, 5) and potassium iodide. Removal of a methylene proton from the (tCCH 2 -) bridge with KOBu t forms a monoanion containing a putative carbene moiety. Oxidation of the anion with iodine leads to net hydride removal and yields the unusual C 2 -bridged dimers Tp′(CO) 2 MtCCtW(CO)(PhCtCPh)Tp (M ) Mo , 7; W, 8). Conversion of the tungsten-carbon single bond in the precursor complex to a triple bond in the product is accompanied by a significant reduction in donation to the metal from the alkyne π ⊥ orbital.

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Formation of Derivative Carbyne Complexes from Tp‘(CO)₂M⋮CCH₃ (M = Mo, W)

Cited by 37 publications

References 30 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Variable Electronic Coupling through Hydrocarbon Spacers Bridging Metal−Carbon Triple Bonds

Deprotonation and Oxidation of the W⋮CCH₂−W Bridge To Form a C₂-Biscarbyne W⋮C−C⋮W Bridge

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Formation of Derivative Carbyne Complexes from Tp‘(CO)2M⋮CCH3 (M = Mo, W)

Cited by 37 publications

References 30 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Variable Electronic Coupling through Hydrocarbon Spacers Bridging Metal−Carbon Triple Bonds

Deprotonation and Oxidation of the W⋮CCH2−W Bridge To Form a C2-Biscarbyne W⋮C−C⋮W Bridge

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Formation of Derivative Carbyne Complexes from Tp‘(CO)₂M⋮CCH₃ (M = Mo, W)

Deprotonation and Oxidation of the W⋮CCH₂−W Bridge To Form a C₂-Biscarbyne W⋮C−C⋮W Bridge