DIE CHEMISCHE VERSCHIEBUNG DES ZWEIFACHKOORDINIERTEN PHOSPHORS, I<sup>1</sup>

Lochschmidt, Siegfried; Schmidpeter, Alfred

doi:10.1080/03086648708072843

Cited by 69 publications

(27 citation statements)

References 110 publications

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“…While such In analogy to the halides, alkyl compounds of electropositive elements also add at the P=N double bond. Thus, reaction of 3 with BMe, smoothly affords the 1,2-addition product 86, while the partly alkylated aminoiminophosphane 15 …”

Section: Halometalation and Organometalation Reactionsmentioning

confidence: 99%

Iminophosphanes: Unconventional Compounds of Main Group Elements

Niecke¹,

Gudat²

1991

Angew. Chem. Int. Ed. Engl.

143

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Dedicated to Professor R o y Appel on the occasion of his 70th birthdayThe large number of known stable compounds in which phosphorus has a low coordination number makes it clear that such compounds can no longer be regarded as "exotic" in main group chemistry. While the rich chemistry of P-C multiply bonded systems makes clear their affinity to their organic congeners, iminophosphanes in particular are also of increasing importance. The linkage of a phosphinidine fragment with an imine fragment via a multiple bond gives rise to a class of compounds with an unusually wide range of structural types. This in turn leads to a broad spectrum of chemical behavior which makes iminophosphanes extremely useful synthetic building blocks in organoelement chemistry.

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Section: Halometalation and Organometalation Reactionsmentioning

confidence: 99%

Iminophosphanes: Unconventional Compounds of Main Group Elements

Niecke¹,

Gudat²

1991

Angew. Chem. Int. Ed. Engl.

143

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“…However, the observation of a relatively large indirect 3 1~, 3 1~ spin-spin coupling for this compound is counterintuitive, indicating that there is, nevertheless, a strong communication of nuclear spins via the electronic framework. For comparison, in the donor-stabilized meth lenediylphos-?I phenium cation [R2C=P-PPh3If, the I ' J (~~P , P)I has been reported as 450.5 Hz; however, the P-P separation is about is negative in compounds with phosphorus in low coordination environments (2,4,5).…”

Section: Resultsmentioning

confidence: 99%

“…Since the C-N-P bond angle is approximately linear, 169S0, it is reasonable to assume that the electric field gradient at the nitrogen centre will be nearly axially symmetric, with the largest component along the formal PN triple bond. From the known internuclear separation, rpTN = 1.486 (4) A (12), the dipolar coupling constant, R(1,S) = (p,d4.rr)(y,ysl r,,s3)(~/2.rr), can be calculated, 1070 Hz. With these values, analysis of the asymmetric doublets yields an upper limit for I ' J (~~P , '~N ) I of 25 Hz and a nitrogen nuclear quadrupolar coupling constant, X('~N), of -1.7(2) MHz.…”

Section: Resultsmentioning

confidence: 99%

“…The magnitudes of 3 '~, 3 '~ spin-spin coupling constants between directly bonded phosphorus nuclei, ~J (~~P ,~' P ) , have been reported for numerous compounds (1)(2)(3)(4)(5). Although the ter couplings cover a wide range, (-)232 Hz to (-)684 Hz, and it has been suggested that 'J(~'P,~'P) in these systems increases (i.e., becomes more negative) with increasing phosphorus-phosphorus bond order (4,5,11).…”

Section: Introductionmentioning

confidence: 99%

“…Although the ter couplings cover a wide range, (-)232 Hz to (-)684 Hz, and it has been suggested that 'J(~'P,~'P) in these systems increases (i.e., becomes more negative) with increasing phosphorus-phosphorus bond order (4,5,11).…”

Section: Introductionmentioning

confidence: 99%

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An unusually large value of¹J(³¹P,³¹P) for a solid triphenylphosphine phosphadiazonium cationic complex: determination of the sign ofJfrom 2D spin-echo experiments

Eichele¹,

Wasylishen²,

Schurko³

et al. 1996

Can. J. Chem.

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Phosphorus-3 1 NMR spectra of a solid triphenylphosphine phosphadiazonium salt, [Mes*NP-PPh3:I[S03CF3], have been acquired at 4.7 and 9.4 T. Analysis of the spectra obtained with magic-angle spinning indicates that the two phosphorus nuclei are strongly spin-spin coupled, I'J(~'P,~'P)I = 405(5) Hz, despite the unusually long P-P separation, r,,, = 2.625 A. Twodimensional spin-echo spectra provide convincing evidence that 'J(~'P,~'P) is negative. Semi-empirical molecular orbital calculations at the INDO level support the negative sign for 'J(~'P,~'P). A large span, 576 ppm, is observed for the chemical shift tensor of the two-coordinate phosphorus centre (S,, = 307 ppm, SI2 = 174 ppm, S3, = -269 pprn), which is very similar to the value previously reported for the non-coordinated phosphorus centre in the free Lewis acid, [Mes*NPj [AICl,]. The principal components and orientations of the phosphorus shielding tensors of these compounds are compared with those calculated for [HNP]' and its phosphine adduct using the ab initio Gauge-Including Atomic Orbitals method. The phosphorus chemical shift tensor of the triphenylphosphine moiety has a relatively small span of 33 ppm.Key words: spin-spin coupling constants, solid-state NMR, 3 1~ NMR, MO calculations, phosphadiazonium cation, P-P bonds.RCsumC : Les spectres de la RMN du phosphore-31 du sel de phosphadiazonium de la triphtnylphosphine. [Mes*NPPPh31[S03CF3] ont t t t enregistrt i 4,7 et 9,4 T. L'analyse des spectres obtenus avec la rotation de I'angle-magique indiquent que les deux noyaux de phosphore ont un couplage spin-spin trks fort, I'J(~'P,~'P)I = 405(5) Hz, en dtpit de la longue distance de stparation inhabituelle P-P, r,,, = 2,65 A. Les spectres en deux dimensions spin-Ccho fournissent une preuve convaincante de la valeur negative de 'J(~'P,~'P). Les calculs d'orbitale molCculaire semi empirique au niveau INDO confirment le signe ntgatif de 'J(~'P,~'P). On a observe un graqnd ttalement, 576 ppm, pour le dtplacement chimique du tenseur des deux centre phosphore coordonnts S,, = 307 ppm, S,, = 174 ppm, = -269 ppm, ce quei est trks voisin des valeurs rapporttes anttrieurement pour les centres phosphore non coordonnCes dans les acides de Lewis libres [Mes*NP][AlCl,]. On a compart les composantes principales et les orientations du tenseur de blindage du phosphore avec celles calcultes pour le [HNP]' et ses adduits phosphine en utilisant les calculs ab initio de Gauge incluant la mtthode de l'orbitale atomique. Le dtplacement chimique du tenseur phosphore de l'unitt triphtnylphosphine s'ttale relativement peu 33 ppm.

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