Structure of potassium phosphoramidate

Cameron, T. Stanley; Chan, Carmel T.; Chute, W. J.

doi:10.1107/s0567740880008801

Cited by 22 publications

(19 citation statements)

References 3 publications

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“…cyclo-phosphazanes (1.69-1-75 A) or the monoamidomonothiophosphate anion [1.688 (5)A]. Up to now the longest value found for a P--N bond was that due to the zwitterionic monoamidophosphate anion in the corresponding potassium salt [1.800 (4)A; Cameron, Chan & Chute, 1980]. In this case the nitrogen lone pair is unable to form donor prr(N)---,d'rr(P) bonding because of the additional bonding of a proton.…”

Section: Structure Of the Pyridine Adduct Of Dithiophosphoryl Monochlmentioning

confidence: 99%

Structure of the pyridine adduct of dithiophosphoryl monochloride

Averbuch-Pouchot¹,

Meisel²

1989

Acta Crystallogr C

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Section: Structure Of the Pyridine Adduct Of Dithiophosphoryl Monochlmentioning

confidence: 99%

Structure of the pyridine adduct of dithiophosphoryl monochloride

Averbuch-Pouchot¹,

Meisel²

1989

Acta Crystallogr C

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“…P interactions are weak and variable in distance (cf. N-P single bond distance 1.800(4) Å), 13 18 A pyramidal geometry for phosphorus in 1·dipyr accommodates the non-bonding electron pair and offers interesting comparisons with the hexafluorophosphate salt of phosphonium 4, 2 which involves a distorted octahedral site. The 'bite' (N-P-N) angle in 1·dipyr (75.1(2)°) is substantially less than in 4 (81.7(2)°), due to significantly longer N ?…”

mentioning

confidence: 99%

“…P interactions are weak and variable in distance (cf. N-P single bond distance 1.800(4) Å), 13 but effect extension of the P-O(triflate) cation-anion interaction, which is most pronounced for the ionic material [1•dipyr][OSO 2 CF 3 ]. The chelate complexation of 1 by dipyr, illustrated in Fig.…”

mentioning

confidence: 99%

Nitrogen ligands on a phosphinic Lewis acceptor including a 2,2′-dipyridyl chelate complex

et al. 2000

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In the context of the developing coordination chemistry of lone pair bearing phosphinic centers as acceptors, synthesis and characterisation for new complexes of the phosphadiazonium cation with nitrogen donors are described, including the first dipyridyl chelate.The coordination chemistry of phosphorus(V) as an acceptor is well established 1,2 and is highlighted by hexacoordinated centers such as PF 6 2 and the pyridine complex of PF 5 . 3 The Lewis acidity of phosphines represents a more recent and developing area and demonstrates interesting bonding properties by virtue of the non-bonding electron pair at the acceptor site. Systems 1, 2 and 3, containing coordinatively unsaturated phosphinic centers form complexes with amines, 4-7 phosphines, 8 carbenes 9 and arenes, 10 and an example of a bis-ligand complex has been mentioned. 11 We have now developed the coordination chemistry of the phosphadiazonium cation 1 with nitrogen donors, and have isolated the first chelate complex.Reactions Table 1 in comparison with analogous parameters for related complexes.The N ? P interactions are weak and variable in distance (cf. N-P single bond distance 1.800(4) Å), 13 but effect extension of the P-O(triflate) cation-anion interaction, which is most pronounced for the ionic material

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“…C 2 P(S)±N(SO 2 ) 2 bekannt [5]. Die betreffenden P±N(sp 2 )-Absta È nde liegen im Bereich von 177 bis 184 pm, also in der Na È he des ¹idealenª Einfachbindungswerts von 180,0(4) pm in K[H 3 N(sp 3 )±PO 3 ] [7], wa È hrend bekanntlich in N-phosphorsubstituierten organischen Aminen/Amiden (R)P±NR 2 im allgemeinen stark verku È rzte Bindungen mit d(P±N) = 160±170 pm auftreten [8,9]. Ûber weitere Untersuchungen an N,N-disulfonylierten Phosphor-Stickstoff-Verbindungen wird im folgenden berichtet.…”

Section: Polysulfonylamines CXXIII N-persulfonylated Aminophosphaneunclassified

N-Persulfonylierte Aminophosphane und Diaminophosphane

Weitze

Lange

Hiemisch

et al. 2000

Z. anorg. allg. Chem.

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Sieben Aminophosphane XYPN(SO2R)2 und fünf Diaminophosphane XP[N(SO2R)2]2 (X, Y = Cl, Me, Et, Ph; R = Me, Ph) wurden durch Umsetzung von Chlorphosphanen mit AgN(SO2R)2 oder Me3SiN(SO2Me)2 als hydrolyselabile, gegenüber Luftsauerstoff indifferente Festkörper erhalten. Drei der Monoaminophosphane wurden durch Oxidation mit SO3 in die Phosphanoxide PhnCl2‐nP(O)N(SO2Me)2 (n = 0, 1, 2) überführt. Für sämtliche Verbindungen sind 31P‐ und 1H‐NMR‐Daten angeführt; Et2PN(SO2Me)2 (3 b) zeigt eine bemerkenswert große 1H‐Verschiebungsnichtäquivalenz für die diastereotopen CH2‐Protonen (δδ = 0,62 ppm). Während im Fall der Diaminophosphane die Einkristallzucht mißlang, konnten die Strukturen von Cl2PN(SO2Me)2 (1 a; monoklin, Raumgruppe P21/c, Z = 8, zwei unabhängige Moleküle), Me(Cl)PN(SO2Me)2 (2 a; monoklin, P21/n, Z = 4) und 3 b (monoklin, P21/c, Z = 4) durch Tieftemperatur‐Röntgenbeugung bestimmt werden. Herausragende Aspekte der Molekülstrukturen sind die trigonal‐pyramidale Koordination der P‐Atome (Bindungswinkel ca. 100°), die nahezu planare Konfiguration der N‐Atome, ungewöhnlich lange P–N‐Bindungen (175 pm in 1 a und 2 a, 179 pm in 3 b) sowie kurze intramolekulare 1,4‐Bindungswechselwirkungen zwischen P und einem Sulfonyl‐Sauerstoff (P…O 281, 291 und 302 pm für 1 a, 2 a bzw. 3 b). Die unabhängigen Moleküle von 1 a sind in alternierender Anordnung über zwei schwächere P…O‐Kontakte (312 und 319 pm) zu Ketten verknüpft, so daß den P‐Atomen eine effektive (3 + 2)‐Pentakoordination zukommt. Generell erfahren N,N‐disulfonylierte Aminophosphane in Gegenwart protonenaktiver Substanzen, wie z. B. Alkoholen, eine rasche Spaltung der P–N‐Bindung. Zur Veranschaulichung dieser für Synthesezwecke nützlichen Eigenschaft werden Umsetzungen von Ph2PN(SO2Me)2 mit Thiolen RSH (R = Et, iPr, tBu, Ph, 4‐Chlorphenyl) beschrieben, die in guten Ausbeuten zu den entsprechenden Thiophosphinigsäureestern Ph2PSR führen.

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Structure of potassium phosphoramidate

Cited by 22 publications

References 3 publications

Structure of the pyridine adduct of dithiophosphoryl monochloride

Structure of the pyridine adduct of dithiophosphoryl monochloride

Nitrogen ligands on a phosphinic Lewis acceptor including a 2,2′-dipyridyl chelate complex

N-Persulfonylierte Aminophosphane und Diaminophosphane

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