Chlorophospheniums, precurseurs de nouveaux cations du phosphore dicoordonne

Mazières, Marie‐Rose; Roques, C.; Sanchez, M.; Majoral, J.‐P.; Wolf, Robert

doi:10.1016/s0040-4020(01)86792-2

Cited by 28 publications

(17 citation statements)

References 14 publications

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“…[6b] R 2 C(CN) 2 [9] (R ϭ Me, Benz), (iPr 2 N) 2 PCl, [10] (iPr 2 N) 2 POTf [11] H 5.42, N 6.06; found C 75.13, H 5.61, N 5.91.…”

Section: Methodsmentioning

confidence: 99%

“…The atomic scattering factors were taken from International tables for X-ray crystallography. [16] All hydrogen atoms were located on difference Fourier maps and refined with a riding model, excepted H(31) of 9, 10b and 12b and hydrogens atoms H (11) and H(21) of compound 32, which were refined isotropically. All nonhydrogens atoms were refined anisotropically and a weighting scheme was applied in the last cycles of refinement; weights were calculated from the following formula: w ϭ 1/[σ 2 (F o 2 )ϩ(aP) 2 ϩ bP] where P ϭ (F o 2 ϩ 2F c 2 )/3.…”

Section: Preparation Of 11amentioning

confidence: 99%

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A Straightforward Synthesis of N‐Functionalized β‐Diimines

et al. 2002

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Reaction of Schwartz’s reagent [Cp2ZrHCl]n (1) (one or two equivalents) with gem‐dinitrile compounds of the type X(CN)2 [X = CMe2, CBenz2, P(NiPr2)2] gives the corresponding mono‐ and di‐N‐zirconated imino complexes selectively. Substitution reactions of the zirconocene metal fragment with electrophiles such as, for example, chlorophosphanes of the type R2PCl, acid chlorides RC(O)Cl or the iminium salt [CH2NMe2]Cl allowed the preparation of a large variety of stable N‐functionalized mono‐ and β‐diimine derivatives. The nature of the X group is of particular importance for the success of the substitution reaction step. The X‐ray crystal structures obtained for the N‐functionalized gem‐aldimino‐nitrile compounds 9, 10b, the N‐phosphorylated β‐diimine 32, and the gem‐formyl nitrile derivative 12b are presented. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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“…[6b] R 2 C(CN) 2 [9] (R ϭ Me, Benz), (iPr 2 N) 2 PCl, [10] (iPr 2 N) 2 POTf [11] H 5.42, N 6.06; found C 75.13, H 5.61, N 5.91.…”

Section: Methodsmentioning

confidence: 99%

Section: Preparation Of 11amentioning

confidence: 99%

A Straightforward Synthesis of N‐Functionalized β‐Diimines

et al. 2002

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“…Solvents were dried by standard procedures. Compounds 1 a, [16a] 4 a and 4 c, [22] and 9 and 10 [47] were prepared as described. ); positive signs denote shifts to lower frequencies, and coupling constants are given as absolute values; prefixes i-, o-, m-, p-denote atoms of mesityl substituents.…”

Section: Methodsmentioning

confidence: 99%

Stability and Electrophilicity of Phosphorus Analogues of Arduengo Carbenes—An Experimental and Computational Study

et al. 2000

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A variety of differently substituted 1,3,2-diazaphospholenium salts and P-halogeno-1,3,2-diazaphospholenes (X = F, Cl, Br) were synthesized, and their molecular structures, bonding situation, and Lewis acid properties were characterized by experimental (single-crystal X-ray diffraction, NMR and IR/Raman spectroscopy, MS, conductometry, titrations with Lewis bases) and computational methods. Both experimental and computational investigations confirmed that the structure and bonding in the diazaphospholenium cations of OTf and BF4 salts resembles that of neutral Arduengo carbenes and that the cations should not be described as genuinely aromatic. P-Halogenodiazaphospholenes are, in contrast to earlier assumptions, molecular species with covalent P-X bonds whose bonding situation can be expressed in terms of hyperconjugation between the six pi electrons in the C2N2 unit and the sigma*(P-X) orbital. This interaction induces a weakening of the P-X bonds, whose extent depends subtly on substituent influences and contributes fundamentally to the amazing structural similarity of ionic and covalent diazaphospholene compounds. A further consequence of this effect is the unique polarizability of the P-Cl bonds in P-chlorodiazaphospholenes, which is documented in a considerable spread of P-X distances and bond orders. Measurement of the stability constants for complexes of diazaphospholene compounds with Lewis bases confirmed the lower Lewis acidities and higher stabilities of diazaphospholenium ions as compared with nonconjugated phosphenium ions; this had been inferred from computed energies of isodesmotic halide-transfer reactions, and permitted also to determine equilibrium constants for P-Cl bond dissociation reactions. The results suggest, in accord with conductance measurements, that P-chlorodiazaphospholenes dissociate in solution only to a small extent. On the basis of these findings, the unique solvatochromatic behavior of NMR chemical shifts of these compounds was attributed to solvent-dependent P-Cl bond polarization rather than to shifts in dissociation equilibria.

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“…The methods for preparing Nphosphanyl phosphazenes, known in the literature, are rather complicated [13,14]. Therefore, we studied the possibility and the conditions for preparing compounds of this type using azidophosphanes as reactants.…”

Section: Introductionmentioning

confidence: 99%