Darstellung sowie Kristall‐ und Molekülstruktur von Triphenylphosphinoxidhydrogenfluorid, (C₆H₅)₃PO · HF

Abstract

(C6H5)3PO · HF wurde aus 40% iger Flußsäure und (C6H5)3PO in Benzol dargestellt. Es kristallisiert monoklin in der Raumgruppe P21/c mit a = 1032,8(3), b = 1 051,0(7), c = 1695,5(2) pm, β = 121,95(2)° und Z = 4; d (ber./gef.) = 1,27/1,26 g · cm−3. Die Struktur wurde anhand von 2 709 unabhängigen Reflexen direkt bestimmt und nach der Kleinste‐Quadrate‐Methode (volle Matrix) bis zu einem R‐Wert von 0,049 verfeinert. In der Verbindung sind HF und (C6H5)3PO über eine kurze H‐Brücke verknüpft. Einige Abstände: OF 238,4(5), OH 142,3, HF 99,8, PO 149,5(4) pm. Winkel OHF 159,8°.

Synthesis, Structures and Properties of Cluster Complexes [H3O(Ph3PO)3]2[Mo6Cl14] and [H(Ph3PO)2]2[Re6S6Br8]

“…The interaction of the cluster acid (H 3 O) 2 Figure 1, Figure 2). The lengths of the Mo-Cl 3 ] + ( Figure 3) is a distinctive feature of the structure.…”

“…Mo 6 Cl 12 was synthesized by the method described previously. [22] (H 3 O) 2 [23] Other reagents were purchased from Aldrich and used as received without additional treatment. Elemental analyses (Carlo Erba Instrument EA1106) were performed by the laboratory of microanalysis at the Vorozhtsov Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences.…”

“…The third group combines the compounds in which the Ph 3 PO molecules are bound together by strong symmetrical or non-symmetrical hydrogen bonds, but the anions do not participate in the hydrogen bonding. A typical example of such compounds is (Ph 3 PO) 2 + . [9] The interaction of chloromolybdenic(II) acid (H 3 O) 2 -Mo 6 Cl 14 with triphenylphosphane oxide was first studied by Sheldon, [11] but the reaction products were not described thoroughly enough and their structure was not studied.…”

“…Compounds with the stoichiometry Ph 3 PO/acid = 1:1 are formed for the reactions with HNO 3 , [1] HF, [2] HCl, [3] HBr, [4] CCl 3 COOH. [5] Compounds with a Ph 3 PO/acid ratio of 2:1 are also found -(Ph 3 PO) 2 ·H 2 O·HBr, [6] (Ph 3 PO) 2 ·(CH 3 ) 2 -C(COOH), [7] (Ph 3 PO) 2 ·HAuCl 4 , [8] (Ph 3 PO) 2 ·HClO 4 .…”

Structure of triphenylphosphine oxide hemiperhydrate

“…Recently, we have found short hydrogen bonds in PhaPO. HCI (Haupt, Huber, Kriiger, Preut & Thierbach, 1977), Ph3PO.HF (Thierbach & Huber, 1979a) and (PhaPO) 2. H20.…”