Thiocarbonylphosphorane and arsorane ligands

Burt, Liam K; Hill, Anthony F.; Jones, Stephanie L.

doi:10.1039/d2cc03747e

Chem. Commun.

2022

DOI: 10.1039/d2cc03747e

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Thiocarbonylphosphorane and arsorane ligands

Liam K Burt

Anthony F. Hill

Stephanie L. Jones

Abstract: Independently unstable thiocarbonylphosphorane ligands S=C=PR3 are observed in the salts [W(η2-C,S-SCPR3)(CO)2(Tp)]PF6 [PR3 = PCy3, PMenPh3-n: n = 0, 1, 2; Tp = tris(dimethylpyrazolyl)borate] which arise from the reactions of phosphoniocarbynes...

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2024

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Synthesis and Alkyne Metathesis Activity of Pincer Rhenium Carbyne Complexes

Tsang,

Bai,

Kong

et al. 2024

Organometallics

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While alkyne metathesis reactions involving d 0 carbynes (alkylidynes) are well documented, those involving welldefined non-d 0 carbynes are still rare. This work reports the synthesis and alkyne metathesis activity of d 2 Re(V) carbyne complexes supported by a [LXL]-type monoanionic [PNP]-pincer ligand, a [LLX]-type monoanionic [PNO]-pincer ligand, and a [ON OH ]-bidentate ligand derived from the Schiff base 2-[(2hydroxyphenyl)iminomethyl]phenol. Treatment of Re(� CCH 2 Ph)Cl 2 (PMePh 2 ) 3 (1) with bis(2-diphenylphosphino-4tolyl)amine (PNHP) and 2-{(2-diphenylphosphino-phenyl)-iminomethyl}phenol (PNOH) in the presence of NEt 3 produced the pincer complexes Re(�CCH 2 Ph)Cl(PMePh 2 )(PNP) (2) and Re(�CCH 2 Ph)Cl(PMePh 2 )(PNO) (3), respectively. The Schiff base 2-[(2-hydroxyphenyl)iminomethyl]phenol (HON OH ) reacted with Re(�CCH 2 Ph)Cl 2 (PMePh 2 ) 3 (1) to give Schiff base complex Re(�CCH 2 Ph)Cl(PMePh 2 )(ON OH ) (4) (ON OH = o-O-C 6 H 4 −CH�N-(o-C 6 H 4 OH)) bearing a [ON OH ]-bidentate ligand. The [PNP]-and [PNO]-pincer complexes are catalytically active for homometathesis of neat 1-methoxy-4-(1-propyn-1-yl)benzene at 150 °C, while the complex bearing the [ON OH ]-bidentate Schiff base ligand is catalytically inactive under similar conditions. The energy profiles for metathesis reactions of model pincer rhenium alkyne-carbyne complexes have been calculated with DFT methods.

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Synthesis and Alkyne Metathesis Activity of Pincer Rhenium Carbyne Complexes

Tsang,

Bai,

Kong

et al. 2024

Organometallics

View full text Add to dashboard Cite

show abstract

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Thiocarbonylphosphorane and arsorane ligands

Abstract: Independently unstable thiocarbonylphosphorane ligands S=C=PR3 are observed in the salts [W(η2-C,S-SCPR3)(CO)2(Tp)]PF6 [PR3 = PCy3, PMenPh3-n: n = 0, 1, 2; Tp = tris(dimethylpyrazolyl)borate] which arise from the reactions of phosphoniocarbynes...

Cited by 1 publication

References 54 publications

Synthesis and Alkyne Metathesis Activity of Pincer Rhenium Carbyne Complexes

Synthesis and Alkyne Metathesis Activity of Pincer Rhenium Carbyne Complexes

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Thiocarbonylphosphorane and arsorane ligands

Abstract: Independently unstable thiocarbonylphosphorane ligands S=C=PR3 are observed in the salts [W(η2-C,S-SCPR3)(CO)2(Tp*)]PF6 [PR3 = PCy3, PMenPh3-n: n = 0, 1, 2; Tp* = tris(dimethylpyrazolyl)borate] which arise from the reactions of phosphoniocarbynes...

Cited by 1 publication

References 54 publications

Synthesis and Alkyne Metathesis Activity of Pincer Rhenium Carbyne Complexes

Synthesis and Alkyne Metathesis Activity of Pincer Rhenium Carbyne Complexes

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Product

Resources

About

Abstract: Independently unstable thiocarbonylphosphorane ligands S=C=PR3 are observed in the salts [W(η2-C,S-SCPR3)(CO)2(Tp)]PF6 [PR3 = PCy3, PMenPh3-n: n = 0, 1, 2; Tp = tris(dimethylpyrazolyl)borate] which arise from the reactions of phosphoniocarbynes...