On the Tautomerism of Secondary Phosphane Oxides

Christiansen, Andrea; Li, Chuanzhao; Garland, Marc; Selent, Detlef; Ludwig, Ralf; Spannenberg, Anke; Baumann, Wolfgang; Franke, Robert; Börner, Armin

doi:10.1002/ejoc.201000037

Cited by 107 publications

(83 citation statements)

References 37 publications

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“…As expected based on spectroscopic data [16] and related secondary phosphine oxides [16][17][18][19], the organophosphorus compound 1 exhibits a tetracoordinate geometry. The hydrogen atom H1 was located in the difference map and allowed to freely refine giving a P1-H1 distance of 1.319(17) Å.…”

Section: Resultssupporting

confidence: 77%

“…The 1 H NMR spectrum contained resonances at 6.86 (d, 4 J HP = 3.7 Hz), 2.39, and 2.28 ppm for the meta-aromatic, ortho-methyl, and para-methyl positions of the mesityl groups, respectively. The P-H resonance was identified at 8.55 ppm as a doublet with a coupling constant of 476 Hz, which is typical for P(V) 1 J HP constants [18]. Additional evidence was given by the coalescence of this doublet into a singlet at 8.55 ppm in the 1 H{ 31 P} NMR spectrum.…”

Section: Resultsmentioning

confidence: 91%

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Crystal Structure of Bis(2,4,6-trimethylphenyl)-phosphine Oxide

Veinot

Ramgoolam

Giffin

et al. 2017

Molbank

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Abstract:The single crystal structure of bis(2,4,6-trimethylphenyl)phosphine oxide has been determined. All interatomic distances and angles can be considered normal. The aryl substituents adopt an intermediate configuration when compared to both sterically unhindered (e.g., diphenylphosphine oxide) and congested (e.g., bis(2,4,6-tri-tert-butylphenyl)phosphine oxide) secondary phosphine oxides, illustrating the influence of steric congestion on the molecular structure.

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Section: Resultssupporting

confidence: 77%

Section: Resultsmentioning

confidence: 91%

Crystal Structure of Bis(2,4,6-trimethylphenyl)-phosphine Oxide

Veinot

Ramgoolam

Giffin

et al. 2017

Molbank

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“…It is well documented that electron-rich secondary phosphine oxides exist nearly exclusively in their pentavalent tautomeric form, which prevents them from participating in the photo-oxidation step to give the key P-centered radical intermediates. 13,16 As expected, no desired CÀP bond formation products were detected when dicyclohexylphosphine oxide 2 c and ethyl phenylphosphinate 2 d were utilized under the best reaction conditions (entries 14 and 15).…”

mentioning

confidence: 70%

Room Temperature CP Bond Formation Enabled by Merging Nickel Catalysis and Visible‐Light‐Induced Photoredox Catalysis

Xuan

Zeng

Chen

et al. 2015

Chemistry A European J

178

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A novel and efficient C-P bond formation reaction of diarylphosphine oxides with aryl iodides was achieved by combining nickel catalysis and visible-light-induced photoredox catalysis. This dual-catalytic reaction showed a broad substrate scope, excellent functional group tolerance, and afforded the corresponding products in good to excellent yields. Compared with the previously reported use of photoredox/nickel dual catalysis in the construction of C-C bonds, the methodology described herein was observed to be the first to allow for C-heteroatom bond formation.

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“…[8][9][10] To study the possible catalytic activity of transition metal complexes containing electron-deficient phosphinous acid ligands, the ligating properties of phosphinous acids (R f ) 2 PÀ OH bearing strongly electron-withdrawing and sterically demanding 2,4-bis(trifluoromethyl)phenyl groups are described. BisA C H T U N G T R E N N U N G [2,4-bis(trifluoromethyl)phenyl]phosphane oxide is accessible by applying a known procedure on a multigram scale using commercially available substrates.…”

Section: H T U N G T R E N N U N G Lia C H T U N G T R E N N U N G Gamentioning

confidence: 99%

Air‐Stable Platinum and Palladium Complexes Featuring Bis[2,4‐bis(trifluoromethyl)phenyl]phosphinous Acid Ligands

Kurscheid

Neumann

Stammler

et al. 2011

Chemistry A European J

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Secondary phosphane oxides, R(2)P(O)H, are commonly used as preligands for transition-metal complexes of phosphinous acids, R(2)P-OH (R=alkyl, aryl), which are relevant as efficient catalysts in cross-coupling processes. In contrast to previous work by other groups, we are interested in the ligating properties of an electron-deficient phosphinous acid, (R(f))(2)P-OH, bearing the strongly electron-withdrawing and sterically demanding 2,4-bis(trifluoromethyl)phenyl group towards catalysis-relevant metals, such as palladium and platinum. The preligand bis[2,4-bis(trifluoromethyl)phenyl]phosphane oxide, (R(f))(2)P(O)H, reacts smoothly with solid platinum(II) dichloride yielding the trans-configured phosphinous acid platinum complex trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)]. The deprotonation of one phosphinous acid ligand with an appropriate base leads to the cis-configured monoanion complex cis-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H](-), featuring the quasi-chelating phosphinous acid phosphinito unit, (R(f))(2)P-O-H···O=P(R(f))(2), which exhibits a strong hydrogen bridge substantiated by an O···O distance of 245.1(4) pm. The second deprotonation step is accompanied by a rearrangement to afford the trans-configured dianion trans-[PtCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)](2-). The reaction of (R(f))(2)P(O)H with solid palladium(II) dichloride initially yields a mononuclear palladium complex [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)], which condenses under liberation of HCl to the neutral dinuclear palladium complex [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)]. The equilibrium between the mononuclear [PdCl(2)({2,4-(CF(3))(2)C(6)H(3)}(2)POH)(2)] and dinuclear [Pd(2)(μ-Cl)(2){({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H}(2)] palladium complexes is reversible and can be shifted in each direction by the addition of base or HCl, respectively. Treatment of palladium(II) hexafluoroacetylacetonate, [Pd(F(6)acac)(2)], with a slight excess of (R(f))(2)P(O)H yields the complex [Pd(F(6)acac)({2,4-(CF(3))(2)C(6)H(3)}(2)PO)(2)H]. The quasi-chelating phosphinous acid phosphinito unit, which is formed by the liberation of HF(6)acac, is characterized by a O···O distance of 244.1(3) pm. These transition metal complexes are stable towards air and moisture and can be stored for months without any evidence of decomposition.

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On the Tautomerism of Secondary Phosphane Oxides

Cited by 107 publications

References 37 publications

Crystal Structure of Bis(2,4,6-trimethylphenyl)-phosphine Oxide

Crystal Structure of Bis(2,4,6-trimethylphenyl)-phosphine Oxide

Room Temperature CP Bond Formation Enabled by Merging Nickel Catalysis and Visible‐Light‐Induced Photoredox Catalysis

Air‐Stable Platinum and Palladium Complexes Featuring Bis[2,4‐bis(trifluoromethyl)phenyl]phosphinous Acid Ligands

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