Expanding the phosphorus–carbon analogy: formation of an unprecedented 5-phosphasemibullvalene derivative

Self Cite

As eries of substitutedp hosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligandsi n homogeneous catalytic reactions. While their buried volume (%V bur )w as calculatedt og et insight into the steric properties, [LNi(CO) 3 ]c omplexes werep repared in order to determine the correspondingT olman electronic parameter.E TS-NOCV (extended-transition-staten aturalo rbitalf or chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the s-a nd p-contributions to the LÀMi nteraction. Au I coordinationc ompounds of selected examples were prepared and characterizedb ys ingle crystal X-ray diffraction.Finally,the three classes of P III compounds were successfully used in the Au I -catalyzedc ycloisomerization of N-2propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts.

Section: Resultssupporting

confidence: 66%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Overview on the experimentally(1,3-5, 7, 8)a nd theoretically(2,6)d etermined wavenumbers of the A 1 stretching mode for 1-8.…”

mentioning

confidence: 99%

See 3 more Smart Citations

Phosphinine‐Based Ligands in Gold‐Catalyzed Reactions

Rigo

Habraken

Bhattacharyya

et al. 2019

Self Cite

Cover Feature: Phosphinine‐Based Ligands in Gold‐Catalyzed Reactions (Chem. Eur. J. 37/2019)

Rigo

Habraken

Bhattacharyya

et al. 2019

Self Cite

Once upon a time there was a phosphinine…The heteroaromatic phosphinines are versatile starting materials for the design of new phosphorus‐based ligands. The present manuscript reports on the synthesis of a series of substituted phosphinines and the related 1‐phosphabarrelenes and 5‐phosphasemibullvalene derivatives. The steric and electronic properties of these ligands were evaluated both by means of theoretical and experimental methods. The corresponding gold(I) complexes were subsequently applied in homogeneous Au‐catalyzed cycloisomerization reactions, showing very good activities and selectivities. More information can be found in the Full Paper by C. Müller, et al. on page 8769.

Pyridyl‐Functionalized 1‐Phosphabarrelene: Synthesis, Coordination Chemistry and Photochemical di‐π‐Methane Rearrangement

Bruce

Papke

Ehlers

et al. 2019

Self Cite

Dedicatedtothe element phosphorus on the 350th anniversary of its discovery.Abstract: The [4+ +2] cycloaddition of 2-(2'-pyridyl)-4,6-diphenyl-l 3 -phosphinine with the highly reactive dienophile hexafluoro-2-butyne has been studied and the first pyridylfunctionalized 1-phosphabarrelenew as obtained and structurally characterized. Although monodentate CF 3 -1-phosphabarrelenes show only ap oorc oordination ability,t he chelating nature of the novel P, N-hybrid ligand gives accesst ov arious transition-metal complexes.U pon irradiation with UV light, the pyridyl-functionalized 1-phosphabarrelene undergoes ar ather selective di-p-methane rearrangementi nt he coordination sphere of the metal center, leading to the formation of ac omplex based on ah itherto unknown pyridylfunctionalized 5-phosphasemibullvalene derivative.D FT calculations provide first insights into the mechanism of this reaction.[a] Dr.M.B ruce, Dr.M .P apke,M.W eber,Prof.