Is the1JPSeCoupling Constant a Reliable Probe for the Basicity of Phosphines? A31P NMR Study

Beckmann, U.; Süslüyan, Diyana; Kunz, Peter C.

doi:10.1080/10426507.2010.547892

Cited by 82 publications

(98 citation statements)

References 26 publications

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“…For both, SeP(CH 2 OH) 3 and [Se 2 P(CH 2 OH) 2 ] -, 77 Se NMR shifts are close to those of other known phosphine selenides and diselenophosphinates [37,38]. For SeP(CH 2 OH) 3 , the spin-spin constant J P,Se = 677 Hz is lower than most double P=Se bonds (-800 to -1200 Hz) and higher than most single P-Se bonds (-200 to -600 Hz) [39], which goes in line with other phosphine selenides [37], while, for [Se 2 P(CH 2 OH) 2 ] -, J P,Se = 582 Hz is close to the upper bound for J P,Se values for single P-Se bonds, which is, again, common for diselenophosphinates [38].…”

Section: Resultssupporting

confidence: 66%

“…For SeP(CH 2 OH) 3 , the spin-spin constant J P,Se = 677 Hz is lower than most double P=Se bonds (-800 to -1200 Hz) and higher than most single P-Se bonds (-200 to -600 Hz) [39], which goes in line with other phosphine selenides [37], while, for [Se 2 P(CH 2 OH) 2 ] -, J P,Se = 582 Hz is close to the upper bound for J P,Se values for single P-Se bonds, which is, again, common for diselenophosphinates [38]. Although THP has been known and used as ligand for quite a long time, its place on the scale of phosphines donor-acceptor properties [40] was not clear up until now.…”

Section: Resultsmentioning

confidence: 91%

“…Although THP has been known and used as ligand for quite a long time, its place on the scale of phosphines donor-acceptor properties [40] was not clear up until now. This may be done on the basis of spin-spin constant J P,Se value [37] (Table 1) placing THP close to PCy 3 , one of the best r-donors among phosphines.…”

Section: Resultsmentioning

confidence: 99%

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Relativistic Effects in NMR of New Prospective Water-Soluble Ligands SeP(CH2OH)3 and H[Se2P(CH2OH)2]

2015

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We present the synthesis of new phosphine selenide SeP(CH 2 OH) 3 and diselenophosphinate H[Se 2 P(CH 2 OH) 2 ] and their characterization with nuclear magnetic resonance (NMR) spectroscopy and quantum chemistry methods. DFT calculations show large relativistic spin-orbit effects in NMR shielding of phosphorus nuclei. We discuss the impact of Se lone pairs and electrons of P-Se and P-C bonds on the 31 P NMR shift and, especially, its relativistic part. The description of P-Se bonds and characterization of electron lone pairs on Se atoms are carried out with the help of natural localized molecular orbitals analysis and topological analysis of electron localization function.

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Section: Resultssupporting

confidence: 66%

Section: Resultsmentioning

confidence: 91%

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Relativistic Effects in NMR of New Prospective Water-Soluble Ligands SeP(CH2OH)3 and H[Se2P(CH2OH)2]

2015

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“…41 Important crystallographic data and refinement details are summarised in 43 We synthesised several series of imidazole-based phosphine ligands in the last few years for biomimetic model complexes and metallo-drugs. 33,34,44,45,46,47 Here, these ligands as well as some new PN ligands, as depicted in Figure 1, were used in CpRu-complexes, which should catalyse the hydration of alkynes. Spectroscopic data of the four new ligands 1c,h-j is summarized in H} NMR shifts of the ligands (δ L ) and the respective ruthenium complexes (δ C ) as well as (Table 3).…”

Section: General Procedures For the Catalytic Hydration Reactionmentioning

confidence: 99%

“…Compounds 1a,b,d -3a,b,d 32,33 and 1h 34 as well as [CpRu(PPh 3 ) 2 Cl] 35 and [CpRu(C 10 H 8 )]PF 6 36 were prepared according to literature procedures. All reactions were carried out in Schlenk tubes under an atmosphere of dry nitrogen using anhydrous solvents purified according to standard procedures.…”

Section: Synthesismentioning

confidence: 99%

Ruthenium piano-stool complexes bearing imidazole-based PN ligands

Kunz

Thiel

Noffke

et al. 2012

Journal of Organometallic Chemistry

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A variety of piano-stool complexes of cyclopentadienyl ruthenium(II) with imidazole-based PN ligands have been synthesized starting from the precursor complexes CpRu(C10H8)]PF6, CpRu(NCMe)(3)]PF6 and CpRu(PPh3)(2)Cl]. PN ligands used are imidazol-2-yl, -4-yl and -5-yl phosphines. Depending on the ligand and precursor different types of coordination modes were observed; in the case of polyimidazolyl PN ligands these were kappa P-1-monodentate, kappa P-2,N-, kappa N-2,N-and kappa N-3,N,N-chelating and mu-kappa P:kappa N-2,N-brigding. The solid-state structures of CpRu(1a)(2)Cl]center dot H2O (5 center dot H2O) and CpRu(mu-kappa(2)-N,N-kappa('1)-P-2b)(2)](C6H5PO3H)(2)(C6H5PO3H2)( 2), a hydrolysis product of the as well determined CpRu(2b) (2)](PF6)(2)center dot 2CH(3)CN (7b center dot 2CH(3)CN) were determined (1a = imidazol-2-yldiphenyl phosphine, 2b = bis(1-methylimidazol-2-yl) phenyl phosphine, 3a = tris(imidazol-2-yl) phosphine). Furthermore, the complexes CpRu(L) (2) [e] Anorganisch-Chemisches Institut, Universität Zürich-Irchel, Winterthurerstr. 190, CH-8057 Zürich, Switzerland.[ ‡] X-ray structure analysis.

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Organic Compounds Containing Bonds between Se or Te with P, As, Sb and Bi

Murai

2014

Patai's Chemistry of Functional Groups

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This chapter describes syntheses, structures, and reactions of the compounds with phosphorus‐selenium double bonds and with at least one carbon‐phosphorus single bond and of their heavier congeners. Among them, phosphane selenides have been the most deeply studied and used as Lewis base catalysts, metal ligands, molecular sensors, and stating materials leading to selenium‐containing nanoparticles. The coupling constants between the phosphorus and selenium atoms are informative on the basicity of the phosphanes. Phosphinoselenoic acid chlorides and secondary phosphanes are frequently used precursors to give a range of phosphinoselenoic acid derivatives, whereas selenation of dichlorophosphanes leads to phosphonoselenoic acid dichlorides, which are converted to a variety of acid derivatives. The selenation of phosphinites also gives phosphinoselenoic acid O ‐esters. Stereochemical course of the substitution reaction at P ‐chiral phosphorus center in the substitution reaction has been elucidated. Some reactions of dimers of diselenoxophosphanes such as Woollin's reagent are also shown. The chapter finally describes examples of phosphane tellurides, arsenic, antimony, and bismuth isologues of phosphane selenides, although these are fewer.

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Is the¹J_PSeCoupling Constant a Reliable Probe for the Basicity of Phosphines? A³¹P NMR Study

Cited by 82 publications

References 26 publications

Relativistic Effects in NMR of New Prospective Water-Soluble Ligands SeP(CH2OH)3 and H[Se2P(CH2OH)2]

Relativistic Effects in NMR of New Prospective Water-Soluble Ligands SeP(CH2OH)3 and H[Se2P(CH2OH)2]

Ruthenium piano-stool complexes bearing imidazole-based PN ligands

Organic Compounds Containing Bonds between Se or Te with P, As, Sb and Bi

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