Evidence for a plastic crystalline phase in closo-N- methylphosphorimide and closo-N-methylarsenimide

Postel, M.; Casabianca, Francis.; Riess, Jean G.

doi:10.1016/s0020-1693(00)81938-6

Cited by 10 publications

(6 citation statements)

References 6 publications

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“…H310BPF3 + H3uBCO it H3!1BPF3 + H3'°BCO exchange (0) 10B2H6 + "B2H6 it210B"BH6 exchange (7) However, since our objective was to establish general trends for this class of reactions rather than to obtain precise rate constants for any specific step, we postulated that H/D isotope effects introduce only small perturbations as long as the B-H and B-D bonds remain intact.3 Reactions ß and y are essentially equivalent to (8) and (9), respectively; the analogue of (a) is (4). In several cases we measured both the forward and the reverse rate constants; in most cases rate data in one direction were recorded and the reverse rate was deduced from the equilibrium constant.…”

Section: Resultsmentioning

confidence: 99%

Smooth oxidation of phosphorus closo-type compounds. Preparation and characterization of the closo-hexa-N-methyloxythiophosphorimides P4(NMe)6SnO4-n (n = 0-3) and an improved synthesis for the closo-hexa-N-methylthiophosphorimides

Casabianca¹,

Pinkerton²,

Riess³

1977

Inorg. Chem.

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Section: Resultsmentioning

confidence: 99%

Smooth oxidation of phosphorus closo-type compounds. Preparation and characterization of the closo-hexa-N-methyloxythiophosphorimides P4(NMe)6SnO4-n (n = 0-3) and an improved synthesis for the closo-hexa-N-methylthiophosphorimides

Casabianca¹,

Pinkerton²,

Riess³

1977

Inorg. Chem.

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“…We also recently reported the plastic behavior of tetraphosphorus hexa-iV-methylimide, P4(NCH3)6, in the 329-395 K temperature range, and of the structurally related arsenimide, As4(NCH3)6, between 346 and 393 K. 15 Concerning the tetraphosphorus hexa-iV-methylimide tetrasulfides and tetraoxides, P4(NCH3)6S4 and P4(NC-H3)604, no plastic phases were detected up to 423 K; unfortunately both compounds start decomposing around this temperature, thus precluding any investigation nearer to the melting points (519 and 448 K, respectively).…”

Section: Resultsmentioning

confidence: 94%

Plastic phases in globular phosphorus compounds. A new structural criterion for plastic behavior

Postel¹,

Riess²

1977

J. Phys. Chem.

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Somewhat similar values would be found for = 4 if the low temperature results were given more weight than high temperature ones.Fletcher and Heller7 reported for the cyclization of the 1-octanol tetramer is n-decane AH°c = -3.8 kcal/mol and AS°c = -11.2 cal/deg mol. The agreement between the two sets of data is within the experimental uncertainty. ConclusionsThe results obtained in this study confirm the assignment made in our previous works, namely, that the excess ultrasonic absorption of alcohol solutions in cyclohexane is due to the formation of noncyclic tetramers or pentamers. The values of the activation enthalpy and entropy for the association of one alcohol molecule to an (nl)-mer confirm that this reaction is diffusion controlled. The activation enthalpy and entropy for the dissociation of an alcohol molecule from the stable noncyclic n-mer have been obtained for the first time. These two quantities are positive. The equilibrium thermodynamic quantities for the formation of noncyclic and cyclic species have also been obtained. They are in agreement with those determined by "equilibrium" measurements.Supplementary Material Available: Tables of raw ultrasonic absorption data (3 pages). Ordering information is given on any current masthead page.

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“…Ce composé ne peut donc pas être utilisé pour la formation de clathrate. Le terme de composé closo proposé par Postel et al (1976) parait donc plus justifié que celui de composé cage.…”

Section: Description De La Structure Et Discussionunclassified

Synthèse, structure cristalline et moléculaire du trimethyl-4,6,9 hexaza-1,3,4,6,7,9 phospha-5 tricyclo [3.3.1.1^3,7] decane

Jaud¹,

Benhammou²,

Majoral³

et al. 1982

Zeitschrift Für Kristallographie - Crystalline Materials

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Reçule 16 novembre 1981Hexaaza phospha adamantane / Crystal structure / Synthesis Abstract. The title compound C 6 H 15 N 6 P has been synthesized. Its structure has been determined by X-ray single crystal methods. Crystals are monoclinic, space group P2i/n with a = 8.742(11)A, b = 11.342(4)Â, c = 10.209(12)Â, β = 90.28(6)°, Ζ = 4, V = 1012(1)Â 3 , ρ" ρ = 1.3g/cm 3 , ρ χ = 1.32 g/cm 3 , μ(λ) = 2.44cm" \ f(OOO) = 432. There is a C 3 axis in the molecule but not in the crystal. The structure suggests that phosphorus is involved in bonding to adjacent atoms largely via its 3p orbitale and that the lone pair is largely in the 3 s orbital. The pyramidal coordination of the a nitrogen atoms and the relation structure -reactivity is discussed.Dans le cadre d'une étude générale de la réactivité des phosphorhydrazides, des dérivés tricycliques du phosphore tétracoordonné possédant une structure qui s'apparente à celle de l'adamantane ont été synthétisés. χ ρ X = 0 2, X = S 3, X = doublet libre L'analogue à atome de phosphore tricoordonné 3 présentant une faible réactivité par rapport aux dérivés du phosphore tricoordonné à même Brought to you by |

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Evidence for a plastic crystalline phase in closo-N- methylphosphorimide and closo-N-methylarsenimide

Cited by 10 publications

References 6 publications

Smooth oxidation of phosphorus closo-type compounds. Preparation and characterization of the closo-hexa-N-methyloxythiophosphorimides P4(NMe)6SnO4-n (n = 0-3) and an improved synthesis for the closo-hexa-N-methylthiophosphorimides

Smooth oxidation of phosphorus closo-type compounds. Preparation and characterization of the closo-hexa-N-methyloxythiophosphorimides P4(NMe)6SnO4-n (n = 0-3) and an improved synthesis for the closo-hexa-N-methylthiophosphorimides

Plastic phases in globular phosphorus compounds. A new structural criterion for plastic behavior

Synthèse, structure cristalline et moléculaire du trimethyl-4,6,9 hexaza-1,3,4,6,7,9 phospha-5 tricyclo [3.3.1.1^3,7] decane

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Evidence for a plastic crystalline phase in closo-N- methylphosphorimide and closo-N-methylarsenimide

Cited by 10 publications

References 6 publications

Smooth oxidation of phosphorus closo-type compounds. Preparation and characterization of the closo-hexa-N-methyloxythiophosphorimides P4(NMe)6SnO4-n (n = 0-3) and an improved synthesis for the closo-hexa-N-methylthiophosphorimides

Smooth oxidation of phosphorus closo-type compounds. Preparation and characterization of the closo-hexa-N-methyloxythiophosphorimides P4(NMe)6SnO4-n (n = 0-3) and an improved synthesis for the closo-hexa-N-methylthiophosphorimides

Plastic phases in globular phosphorus compounds. A new structural criterion for plastic behavior

Synthèse, structure cristalline et moléculaire du trimethyl-4,6,9 hexaza-1,3,4,6,7,9 phospha-5 tricyclo [3.3.1.13,7] decane

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Synthèse, structure cristalline et moléculaire du trimethyl-4,6,9 hexaza-1,3,4,6,7,9 phospha-5 tricyclo [3.3.1.1^3,7] decane