Gallophosphonates Containing Alkali Metal Ions. 2.¹ Synthesis and Structure of Gallophosphonates Incorporating Na⁺ and K⁺ Ions

Abstract

The reactions between t-BuP(O)(OH)(2) and equimolar quantities of MGaMe(4) (M = Na, K) yield ionic and alkali metal containing molecular gallophosphonates [Na(4)(&mgr;(2)-OH(2))(2)(THF)(2)][(Me(2)GaO(3)PBu-t)(2)](2).2THF (2) and [K(THF)(6)][K(5)(THF)(2){(Me(2)GaO(3)PBu-t)(2)}(3)] (3), respectively. Compounds 2 and 3are soluble in common organic solvents and have been characterized by means of analytical and spectroscopic techniques, as well as by single-crystal X-ray diffraction studies. These compounds represent the rare examples of molecular ionic phosphonate cages which contain coordinated Na(+) or K(+) ions. Compound 2 is constructed from two eight-membered Ga(2)O(4)P(2) gallium phosphonate rings which sandwich a central Na(4)(H(2)O)(2) unit. In the case of 3, three eight-membered Ga(2)O(4)P(2) gallium phosphonate units envelope an aggregated K(5) core which exists in the form of a trigonal-bipyramidal polyhedron. The Na(+) and K(+) ions in 2 and 3 are also coordinated by the endocyclic oxygen atoms of the eight-membered gallophosphonate crowns, apart from the regular exocyclic P-O coordination. Unlike the lithium gallophosphonate [Li(4)(THF)(4)][{(MeGaO(3)PBu-t)(3)(&mgr;(3)-O(2))}(2)] (1), compounds 2 and 3 do not undergo any clean cage conversion reaction in the presence of 15-crown-5 and 18-crown-6, respectively.

Synthesis and structure of 1-D Na6cluster chain with short Na–Na distance: Organic like aromaticity in inorganic metal cluster

“…6b Roesky and coworkers, have also observed, similar but slightly longer Na….Na contacts in galophosphonates containing sodium ions. 4 Another, interesting feature of the 1D chain is that, the hexagonal ring (Na 6 ) is almost planer like benzene {∠Na1 Na1 Na2 = 123.83 (4) and ∠Na2 Na1 Na2 = 112.34 (8) }. It is interesting that the carboxylate groups in the metaloligand acts as a bridge between Mo and the Na centre of the neighbouring polymeric units and forms a porous 3D network (Figure 2b).…”

“…2,3 In recent years bimetallic compounds containing alkali metal clusters have been synthesized. 1a For example, gallium phosphonates have been shown to form cages containing lithium, 1a sodium, and potassium 4 ions with short metal-metal contacts. In the lithium compound the lithium ions are arranged in a finite unidimensional wire.…”

“…These compounds are potential precursors for preparation of ion conductors and molecular sieves. 1a We have been interested in alkali metal complexes of molybdenum containing metalloligands and recently reported synthesis and structure of [{Na 4 H 2 O] n . 5 We were interested in exploring methods for assembly of larger cluster.…”

Untersuchungen zum Reaktionsverhalten von Organometallophosphonaten gegenüber Tetra-n-butylammoniumhydrogendifluorid

“…-Gallanaten dargestellt, besitzen jedoch komplexere Grundgerüste. [42,43,[56][57][58][59] Ziel dieser Arbeit war, das Reaktionsverhalten von Metallophosphonaten gegenüber dem Fluorierungsreagens Tetra-n-butylammoniumhydrogendifluorid zu untersuchen. treten zwei sehr starke Absorptionsbanden in der Region um 1080 cm -1 auf, die versuchsweise ν (P-O-Al)-Schwingungen zugeordnet wurden.…”

“…Der Wert der chemischen Verschiebung entspricht den Signalen von tBuPO 3 -Gruppen in ionisch aufgebauten Gallophosphonaten, die zwischen 26 und 33 ppm liegen. Die neutralen tetrameren Spezies zeigen Verschiebungen um 21 ppm [36][37][38]45,57,58]. Das IR-Spektrum zeigt im Gegensatz zu den literaturbekannten kubischen Metallophosphonaten der Elemente der 13.…”