The investigation of the electronic structure of polyfluoroaromatic phosphines by means of x-ray fluorescent and ultraviolet (He I) photoelectron spectroscopy

Krupoder, S. A.; Fürin, G. G.; Yakobson, G. G.; Dolenko, G. N.; Mazalov, L. N.; Sultanov, A. Sh.; Furley, I. I.

doi:10.1016/s0022-1139(00)81147-1

Cited by 15 publications

(4 citation statements)

References 49 publications

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“…Dewar [17] and Rabalais [15], in their photoelectron spectroscopic work, assume significant p-r interaction. Krupoder his study based on X-ray fluorescent spectroscopy [18], has also found this interaction relatively effective. Further confusion seems to exist concerning the steric structure of phenylphosphine.…”

Section: Introductionmentioning

confidence: 88%

The photoelectron spectrum and conformation of phenylphosphine and phenylarsine

et al. 1995

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He(I) and He(II) photoelectron spectra of phenylphosphine and phenylarsine have been investigated and assigned. The rotational barrier of the phosphino group has been investigated at the MP2/6-31G(d,p)//MP2/6-3 IG(d,p) and HF/6-31G(d,p)//HF/6-3 IG(d,p) levels of theory, and that of the arsino group at the HF/6-3 IG(d,p)//6-31G(d,p) levels of theory. The rotational barrier of the two molecules is nearly the same. The energy difference between the two possible conformers of the molecules is low (1.5 kJ/mol at the MP2/6-31G(d,p) level of theory), allowing nearly free rotation about the P--C bond. The photoelectron spectrum cannot be interpreted by considering the most stable rotamer, but all possible conformers should be taken into account. The present interpretation is consistent with the small np-r interaction concluded from other investigations. The rotational barrier of o-phosphinophenol is significantly larger than for phenylphosphine, and the photoelectron spectrum of this compound can be interpreted by considering a single conformer, and no appreciable interaction between the r-system of the ring and the phosphorus lone pair.

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Section: Introductionmentioning

confidence: 88%

The photoelectron spectrum and conformation of phenylphosphine and phenylarsine

et al. 1995

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“…C 6 F 5 P(NEt 2 ) 2 was reported already in the 1960s 25 , 26 and since then became a subject of occasional physicochemical studies, 27 – 29 which contrasts with the rich chemistry of its nonfluorinated analogue, PhP(NEt 2 ) 2 . Here we report a straightforward and practical alternative to the original synthetic procedure and further investigations into the coordination and catalytic chemistry of C 6 F 5 P(NEt 2 ) 2 in standard model reactions.…”

Section: Introductionmentioning

confidence: 99%

Bis(diethylamino)(pentafluorophenyl)phosphane – a Push–Pull Phosphane Available for Coordination

et al. 2011

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A facile large-scale synthesis of the “push–pull”-substituted ligand bis(diethylamino)(pentafluorophenyl)phosphane is reported. A selenophosphorane as well as complexes with CuI and PdCl2, can be formed almost quantitatively from suitable starting materials. The PdII complex shows a square-planar coordination with significant distortions of the Cl–Pd–Cl moiety in the solid state. In contrast, the phosphane ligand exhibits a large flexibility in the trigonal-planar coordination of the Cu salt, as proven by X-ray crystallography. C–C cross-coupling reactions and 1,3-dipolar cycloadditions have been tested for the PdII and CuI complexes, respectively. Whereas the reactivity of the PdII complex is good at low temperature, the CuI complex reveals remarkable reaction rates at temperatures up to 130 °C. Furthermore, the CuI-catalyzed azide/alkyne 1,3-dipolar cycloaddition was successfully adapted for flow conditions.

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“…The relation between IP(PX 3 ) and IP(HX) is linked to the parallel manifestation of the inductive effect of the substituent X and the mixing of the orbitals Ip and «x- 40 Thus the contribution of the 3/J AO LP of phosphorus to the HOMO increases in the sequence C6F 5 P(NEt 2 )2 < C 6 F 5 P(NCS) 2 < C 6 F 5 P(OMe) 2 in conformity with the increase in the IP,(HX):HNEt 2 (8.15) < HNC (9.94) < HOMe (10.96). 41 The IP(n P ) for the phosphites 2,4, and 5 exceed those for the phosphonites enumerated, like the IP(«o) of fluorinated alcohols, so that the contribution of the phosphorus 3/> AO to the HOMO increases, with an overall increase in IP(np), on passing from the phosphites P(OR)3 and the phosphonites C 6 F 5 PX 2 to the fluorinated phosphites 2,4, and 5 and P(OC 6 F 5 ) 3 . Under these conditions, the np orbital to which the 3 P AO of phosphorus contributes significantly (from 75% to 87% according to different estimates), 40 is also capable of n P -o-£_ o conjugation.…”

Section: The Influence Of Fluorine-containing Substituents On Thementioning

confidence: 99%

“…An appreciable delocalisation of the np electrons has been noted for the compound P(OC6Fs)3, which has been investigated by X-ray emission spectroscopy (PKp). 41 The enhancement of the electron-accepting properties of the ORF substituents via the CTI mechanism is accompanied by an increase in the electrophilicity of the P-O cr*-bonds, the electron deficiency occurring predominantly on the phosphorus atom, because it is less electronegative than oxygen. Bearing in mind the electronic interaction occurring in the O -CH 2 -CF3 fragment and enhancing the electron-accepting properties of the orbital Gco, one may postulate that the conjugation of the P-O <r*-bond and the no electrons, characteristic of the usual P(III) compounds, is unlikely in compounds with this fragment.…”

Section: The Influence Of Fluorine-containing Substituents On Thementioning

confidence: 99%

Fluoroalkoxy-derivatives of trivalent phosphorus: synthesis and reactivity

Миронов¹,

Konovalova²,

Burnaeva³

et al. 1996

Russ. Chem. Rev.

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ContentsI. Introduction 935 II. The influence of fluorine-containing substituents on the properties of the P(III) atom. Photoelectron 935 spectroscopic and electrochemical data III. Synthesis of fluoroalkoxy-derivatives of P(III) 938 IV. Reactions of fluoroalkyl phosphites 948 V. Conclusion 966 Abstract. The review surveys and gives a systematic account of the electronic structures, syntheses, and chemical properties of fluoroalkyl derivatives of trivalent phosphorus (phosphites, thiophosphites, and amidophophites). The methods of preparation and reactivities of fluoroalkyl phosphites are compared with those of unsubstituted phosphites. The bibliography includes 420 references.

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The investigation of the electronic structure of polyfluoroaromatic phosphines by means of x-ray fluorescent and ultraviolet (He I) photoelectron spectroscopy

Cited by 15 publications

References 49 publications

The photoelectron spectrum and conformation of phenylphosphine and phenylarsine

The photoelectron spectrum and conformation of phenylphosphine and phenylarsine

Bis(diethylamino)(pentafluorophenyl)phosphane – a Push–Pull Phosphane Available for Coordination

Fluoroalkoxy-derivatives of trivalent phosphorus: synthesis and reactivity

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