Dibasic character of a bicyclic aminophosphane. Formation and crystal structure of H3B.P(OCMe2CH2)2N.BH3

Grec, Dominique; Hubert‐Pfalzgraf, Liliane G.; Grand, André; Riess, Jean G.

doi:10.1021/ic00220a043

Cited by 24 publications

(5 citation statements)

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“…When for example the frequency of the v(C0) vibrations of M(CO),L adducts are measured-a commonly used approach to probe the a-accepting ability of a ligand L-one observes that these frequencies are significantly higher than L = 1 than with related but acyclic phosphorus ligands reputed to be strongly Ir-acid (Scheme 17). [22][23][24][25][26][27][28]29 This again is in line with the p,-d, rationale: the overlap of the orbitals concerned being expected to be less effective when nitrogen is pyramidal, the a-acid character of the phosphorus with respect to the metal should be enhanced; but the strain imposed on the angles at phosphorus is also expected to influence this character.…”

Section: Effects Of the Nitrogen Atom On The Donor Character Of The Psupporting

confidence: 54%

“…effectively zero, since in the latter case the nitrogen's lone pair is no longer available for a-bonding. 22 conciliate this with the large decrease in P-N bond length (0.07 A) observed between l l c and the solely P-coordinated complex 221 It is also difficult to reconcile the total absence of Np,-Pd, interaction with the low coordination ability of this pyramidal nitrogen towards transition metals, even in their high oxidation states.…”

Section: Effects Of the Nitrogen Atom On The Donor Character Of The Pmentioning

confidence: 96%

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About the Coordination Chemistry of the Phosphorus-Nitrogen Entity

Riess

1986

Phosphorous and Sulfur and the Related Elements

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Triply coordinated trivalent nitrogen atoms are known to lose most or all of their Lewis donor capacity when bonded to a third or higher row element. It is shown here, in the case of P-bonded nitrogen atoms, that structural constraints which maintain the nitrogen atom in a pyramidal configuration can contribute much in preserving their basicity and/or nucleophilic character. In particular, nitrogen atoms apically bonded to 5-coordinated formally penta-or trivalent phosphorus atoms can display definite basicity. Examples of metal-and base-induced opening and closing of P-N bonds are also presented. The following unusual coordination modes and/or reaction issues are exemplified:where A can be-depending on the case-H+,CH~,BH,,BF, or a transition metal moiety, as for example CpMo(CO),CI or CpMo(CO),, etc. The factors that affect the rather variable P-N bond length are discussed.

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Section: Effects Of the Nitrogen Atom On The Donor Character Of The Psupporting

confidence: 54%

Section: Effects Of the Nitrogen Atom On The Donor Character Of The Pmentioning

confidence: 96%

About the Coordination Chemistry of the Phosphorus-Nitrogen Entity

Riess

1986

Phosphorous and Sulfur and the Related Elements

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“…In order to reduce sensor fouling in the presence of these naturally occurring interferents, our laboratory is exploring the use of sensor membranes made with fluorous matrixes, which exhibit a low solubility for naturally occurring hydrophobic lipids. For example, at 37 °C, stearic acid has a solubility in hexane of 430 mM, whereas in the fluorous solvent trans -1,2-bis(perfluorohexyl)ethylene it has a solubility of only 0.026 mM — over four orders of magnitude lower [27]. …”

Section: Resultsmentioning

confidence: 99%

Preparation of a highly fluorophilic phosphonium salt and its use in a fluorous anion-exchanger membrane with high selectivity for perfluorinated acids

Boswell

Anfang

Bühlmann

2008

Journal of Fluorine Chemistry

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Fluorous solvents are the most nonpolar, nonpolarizable phases known, whereas ions are inherently polar. This makes it difficult to create salts that are soluble in a fluorous solvent. Here we present the synthesis and characterization of a new fluorophilic phosphonium salt, tris{3,5-bis[(perfluorooctyl)propyl]phenyl}methylphosphonium methyl sulfate. The salt has a solubility of at least 14 mM in perfluoro(perhydrophenanthrene), perfluoro(methylcyclohexane), and perfluorohexanes. It also shows immediate potential for use as a phase-transfer catalyst in fluorous biphasic catalysis, but in this work it is used as an anion exchanger site in the first potentiometric fluorous-membrane anion-selective electrode. The membrane sensor exhibited the exceptional selectivity of 3.9 × 1010 to 1 for perfluorooctanesulfonate over chloride, and of 2.5 × 107 to 1 for perfluorooctanoate over chloride. With improvements to the sensor’s detection limit and lifetime, it has the potential to be an attractive alternative to the expensive, time-consuming methods currently employed for measurement of perfluorinated acids.

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“…The product was recrystallized from methanol-water (90:10) to yield 1.7 g (55% of theoretical yield). Elemental analysis of the product gave the molecular formula C9H24N309P3-H20 (Found: C, 25.52; , 6.04; N, (14) Tikhonova, L. (20) Popov, K. I.; Larchenko, V. E.; Chuvaev, V. F.; Dyatlova, N. M. Zh.…”

Section: Methodsmentioning

confidence: 99%