Fluorocarbyne complexes <i>via</i> electrophilic fluorination of carbido ligands

Hill, Anthony F.; Manzano, Richard A.

doi:10.1039/d3sc00261f

Cited by 3 publications

(2 citation statements)

References 94 publications

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“…Thus, fast sweep rates are required to observe a reasonable degree of reversibility, with, however, an almost identical half-wave potential (E 1 2 0.345 V) to that of 5. Chemical oxidation of tris(pyrazolyl)borate carbyne complexes of tungsten is typically accompanied by decarbonylation [65,[69][70][71], which most likely accounts for the poor reversibility at slow sweep rates or higher voltages.…”

Section: Ligand Installationmentioning

confidence: 99%

Poly(imidazolyliden-yl)borato Complexes of Tungsten: Mapping Steric vs. Electronic Features of Facially Coordinating Ligands

Inglis,

Manzano,

Kirk

et al. 2023

Molecules

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A convenient synthesis of [HB(HImMe)3](PF6)2 (ImMe = N-methylimidazolyl) is decribed. This salt serves in situ as a precursor to the tris(imidazolylidenyl)borate Li[HB(ImMe)3] pro-ligand upon deprotonation with nBuLi. Reaction with [W(≡CC6H4Me-4)(CO)2(pic)2(Br)] (pic = 4-picoline) affords the carbyne complex [W(≡CC6H4Me-4)(CO)2{HB(ImMe)3}]. Interrogation of experimental and computational data for this compound allow a ranking of familiar tripodal and facially coordinating ligands according to steric (percentage buried volume) and electronic (νCO) properties. The reaction of [W(≡CC6H4Me-4)(CO)2{HB(ImMe)3}] with [AuCl(SMe2)] affords the heterobimetallic semi-bridging carbyne complex [WAu(μ-CC6H4Me-4)(CO)2(Cl){HB(ImMe)3}].

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Section: Ligand Installationmentioning

confidence: 99%

Poly(imidazolyliden-yl)borato Complexes of Tungsten: Mapping Steric vs. Electronic Features of Facially Coordinating Ligands

Inglis,

Manzano,

Kirk

et al. 2023

Molecules

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“…The π-activation of unsaturated hydrocarbons, such as alkenes, dienes, alkynes, or allenes, via coinage metals is well-established − and led to numerous methodologies and applications, especially in organic chemistry and catalysis. − Coinage metals are also known to efficiently coordinate to a number of heteroelement-based π-systems, − yet practical applications of the latter still remain limited. Despite the interest of metal–carbon triple bonds in organometallic chemistry, − the activation of MC motifs via external d-block metal centers is still in its infancy.…”

Section: Introductionmentioning

confidence: 99%

π-Bonding of Group 11 Metals to a Tantalum Alkylidyne Alkyl Complex Promotes Unusual Tautomerism to Bis-alkylidene and CO₂ to Ketenyl Transformation

Lachguar,

Del Rosal,

Maron

et al. 2024

J. Am. Chem. Soc.

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A salt metathesis synthetic strategy is used to access rare tantalum/coinage metal (Cu, Ag, Au) heterobimetallic complexes. Specifically, complex [Li(THF) 2 ][Ta(C t Bu)-(CH 2 t Bu) 3 ], 1, reacts with (IPr)MCl (M = Cu, Ag, Au, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) to afford the alkylidyne-bridged species [Ta(CH 2 t Bu) 3 (μ-C t Bu)M(IPr)] 2-M. Interestingly, π-bonding of group 11 metals to the Ta�C moiety promotes a rare alkylidyne alkyl to bis-alkylidene tautomerism, in which compounds 2-M are in equilibrium with [Ta(CH t Bu)-(CH 2t Bu) 2 (μ-CH t Bu)M(IPr)] 3-M. This equilibrium was studied in detail using NMR spectroscopy and computational studies. This reveals that the equilibrium position is strongly dependent on the nature of the coinage metal going down the group 11 triad, thus offering a new valuable avenue for controlling this phenomenon. Furthermore, we show that these uncommon bimetallic couples could open attractive opportunities for synergistic reactivity. We notably report an uncommon deoxygenative carbyne transfer to CO 2 resulting in rare examples of coinage metal ketenyl species, ( t BuCCO)M(IPr), 4-M (M = Cu, Ag, Au). In the case of the Ta/Li analogue 1, the bis(alkylidene) tautomer is not detected, and the reaction with CO 2 does not cleanly yield ketenyl species, which highlights the pivotal role played by the coinage metal partner in controlling these unconventional reactions.

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Carbon–chalcogen wires: alkynyltellurolatocarbynes

Onn,

Hill

2024

Chem. Commun.

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Fluorocarbyne complexes via electrophilic fluorination of carbido ligands

Abstract: The new fluorocarbynes [M(ΞCF)(CO)2(Tp)] (M = Mo, W; Tp = tris(dimethylpyrazolyl)borate) arise from electrophilic fluorination of the the lithiocarbynes [M(ΞCLi)(CO)2(Tp)] with FN(SO2Ph)2. The reactions of [W(ΞCF)(CO)2(Tp)] with [AuCl(SMe2)] and PhICl2 afford...

Cited by 3 publications

References 94 publications

Poly(imidazolyliden-yl)borato Complexes of Tungsten: Mapping Steric vs. Electronic Features of Facially Coordinating Ligands

Poly(imidazolyliden-yl)borato Complexes of Tungsten: Mapping Steric vs. Electronic Features of Facially Coordinating Ligands

π-Bonding of Group 11 Metals to a Tantalum Alkylidyne Alkyl Complex Promotes Unusual Tautomerism to Bis-alkylidene and CO₂ to Ketenyl Transformation

Carbon–chalcogen wires: alkynyltellurolatocarbynes

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Fluorocarbyne complexes via electrophilic fluorination of carbido ligands

Abstract: The new fluorocarbynes [M(ΞCF)(CO)2(Tp*)] (M = Mo, W; Tp* = tris(dimethylpyrazolyl)borate) arise from electrophilic fluorination of the the lithiocarbynes [M(ΞCLi)(CO)2(Tp*)] with FN(SO2Ph)2. The reactions of [W(ΞCF)(CO)2(Tp*)] with [AuCl(SMe2)] and PhICl2 afford...

Cited by 3 publications

References 94 publications

Poly(imidazolyliden-yl)borato Complexes of Tungsten: Mapping Steric vs. Electronic Features of Facially Coordinating Ligands

Poly(imidazolyliden-yl)borato Complexes of Tungsten: Mapping Steric vs. Electronic Features of Facially Coordinating Ligands

π-Bonding of Group 11 Metals to a Tantalum Alkylidyne Alkyl Complex Promotes Unusual Tautomerism to Bis-alkylidene and CO2 to Ketenyl Transformation

Carbon–chalcogen wires: alkynyltellurolatocarbynes

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Product

Resources

About

Abstract: The new fluorocarbynes [M(ΞCF)(CO)2(Tp)] (M = Mo, W; Tp = tris(dimethylpyrazolyl)borate) arise from electrophilic fluorination of the the lithiocarbynes [M(ΞCLi)(CO)2(Tp)] with FN(SO2Ph)2. The reactions of [W(ΞCF)(CO)2(Tp)] with [AuCl(SMe2)] and PhICl2 afford...

π-Bonding of Group 11 Metals to a Tantalum Alkylidyne Alkyl Complex Promotes Unusual Tautomerism to Bis-alkylidene and CO₂ to Ketenyl Transformation