How the Organic Moiety Drives the Coordination Chemistry of Metal Phosphonates: The First Enantiomerically Pure Zinc Phosphonate

Abstract

The first enantiomerically pure metallophosphonate, (R)-gives clear evidence of the critical role played by the organic moiety that fully drives the coordination chemistry of Zn[O 3 PCH 2 P(O)(CH 3 )(C 6 H 5 )]·H 2 O has been prepared. The layered arrangement in this compound is drastically different phosphonic acids with transition metals. from that observed in the racemic series; this observation Metal phosphonate chemistry is undergoing rapid expan-zinc nitrate in water, under neutral-pH conditions, then yielded compound A in 85% yield. To ensure that all the sion, with applications in various areas such as ion exchange, catalysis, sensors, proton conductors, magnetism, crystals of the preparation corresponded to the same enantiomeric form, the specific rotation of compound A (after or photochemically active materials. [1] Furthermore, an attractive feature is their potential for supramolecular as-dissolution in 1  HCl) was measured and found to be identical to that of the isolated resolved phosphonic acid sembly, provided that the structure of the phosphonate framework can be finely tuned by the suitable design of the precursor.The structure consists of layers (ab plane; Figure 1) in RPO 3 H 2 phosphonic acid precursor. For that purpose, it is essential to know, for a given metal, the role played by the which the zinc atoms are tetrahedrally coordinated with three oxygen atoms from the phosphonate groups [ZnϪO: organic moiety R attached to the phosphorus atom [via its shape, its rigidity, and the number and nature of its func-1.891(6)Ϫ1.918(7) Å ] and one oxygen atom from the phosphane oxide moiety [ZnϪO: 1.993(5) Å ]. In each layer, the tional groups], on the structure and dimensionality of the resulting metal phosphonates. In this context, we have re-zinc atoms are arranged in 12-membered rings, constructed by corner-sharing of alternating ZnO 4 and PO 3 C tetra-cently reported the coordination chemistry of phosphonic acids bearing functionalities of various bulks, showing that hedra. The phenyl groups are oriented toward the interlayer space, with a basal spacing (c/2 ϭ 12.65 Å ) shorter than the a control of the dimensionality of zinc phosphonates could be achieved. [2] Another aspect that has never been studied usual 15Ϫ16 Å value observed for layered metal phenylphosphonates, due to a close-packing of the sheets caused is the possibility to get enantiomerically pure phosphonate networks using chiral precursors. In this paper, we report by the interdigitation of the aromatic rings from neighbouring slabs (Figure 2). The lattice water molecules are present the synthesis and structural characterization of the first enantiomerically pure metal phosphonate: (R)-Zn[O 3 PCH 2 P(O)(CH 3 )(C 6 H 5 )] · H 2 O (compound A), based on mixed phosphonic acidϪphosphane oxide chiral building blocks.The phosphonic acid H 2 O 3 PCH 2 P(O)(CH 3 )(C 6 H 5 ) racemate was prepared as previously described [2c] and the optical resolution was performed using quinine to give a 1:1 complex [quinine:H 2 O 3 PCH 2 P(O)(CH 3 )(C 6...

Synthesis and Solid‐State NMR Studies of P‐Vinylbenzylphosphonic Acid

“…Phase B crystallizes in a monoclinic system, and the distance between two layers is increased to 19 Å. The structure of layered Zn phosphonates with intercalated water molecules have been described by Bujoli 1e–1f. Water molecules were interacted weakly through hydrogen bonds with phosphonate oxygen atoms, allowing easy dehydration of the crystal at 30–40 °C.…”

Homochiral Metal−Organic Frameworks Based on Transition Metal Bisphosphonates

“…Notable examples include the use of α,ω-bisphosphonic acids in the synthesis of porous lamellar solids . With a few exceptions, , the use of enantiopure starting materials in the synthesis of porous metal phosphonates has not been investigated. The present work has outlined the design of novel enantiopure bisphosphonates and has successfully shown their potential in the construction of porous homochiral metal phosphonate coordination networks.…”

Role of the catalyst in the synthesis of carbon nanotubes

“…X-ray diffraction has largely contributed to the development of metal phosphonate chemistry, as a direct or indirect method. We will show the significant structure directing role of the organic moiety in this class of organic-inorganic hybrid materials [1]. From our experience in the coordination chemistry of phosphonic acids, we were able to develop applications of metal phosphonates in the field of catalysis and biotechnologies as well.…”

“…A minimal basis is used to obtain a transferable tight-binding parametrization of the C-C, Ni-Ni and Ni-C interactions applicable to binary systems. Using this model, we have investigated the first stages of the nucleation process with Monte Carlo simulations in the grand canonical ensemble and demonstrated the role played by the metal in the dissolution-segregation process of carbon atoms [1].…”