Synthesis and solid state structure of Co(II) complexes of OPTA

Copper(II) and Sodium(I) Complexes based on 3,7‐Diacetyl‐1,3,7‐triaza‐5‐phosphabicyclo[3.3.1]nonane‐5‐oxide: Synthesis, Characterization, and Catalytic Activity

“…The role of water in such an oxidation process was reported by Frost et al . for related systems in which DAPTA was oxidized to DAPTA=O+2 H + .…”

“…The role of water in such an oxidation process was reported by Frost et al [24] for related systemsi nw hich DAPTAw as oxidized to DAPTA = O + 2H + .I no ur case, this oxidation process is presumably combined with the reduction of Cu II (Scheme 3, route 1) or Ni II (Scheme 3, route 2). To prove the role of water in the DAPTAo xidation process, the synthesis of 1 was undertaken under an inert N 2 atmosphere by using freshly dried solvents and 18 O-labeled water (H 2 18 O) in the reactionm edium (see the Experimental Section).…”

“…Several examples are known in which PTA=O binds a metal cation in the O‐, N‐, ON‐, ONN‐, NNN‐, and ONNN‐coordination modes, achieving either discrete metallic units or polymeric compounds. In a number of cases, different types of coordination modes were obtained in the same molecule. For DAPTA=O, however, despite the facts that it has been known for quite a long time and that its structure has already been established, its coordination properties have not yet been studied.…”

“…The oxidizedd erivatives of PTAa nd DAPTA, 1,3,5-triaza-7phosphaadamantane-7-oxide (PTA = O) and 3,7-diacetyl-1,3,7triaza-5-phosphabicyclo[3.3.1]nonane 5-oxide( DAPTA = O), were synthesized for the first time in 1977 by Siele; [11a] the former was prepared by oxidation of PTA, and the latter was prepared by acetylation of PTA = Ow ith acetic anhydride (Scheme 1). Several examples are known in which PTA = O binds am etal cation in the O-, [24,25] N-, [24,26] ON-, [24] ONN-, [27] NNN-, [28] and ONNN-coordinationm odes, [27,29] achieving either discrete metallicu nits or polymeric compounds.I nan umber of cases, [24,26] different types of coordination modes were obtained in the same molecule. For DAPTA = O, however,d espite the facts that it has been known for quite al ong time andt hat its structure has already been established, [11a] its coordination properties have not yet been studied.…”

Molecular Insights into Bulk and Porous κ2P,N‐PTA Metal‐Organic Polymers by Simultaneous Raman Spectroscopy and Inelastic Neutron Scattering

“…Both metal‐organic polymers are constituted from dimetallic units of 1 bridged by {CoCl 3 } – moieties via k 2 N,P coordination of the PTA ligands. It is known that complex‐cobalt units such as {CoCl 3 } – and {Co(NCS) 2 (H 2 O) 2 } can be coordinated via N atoms of the ligand PTA and its derivatives such as O=PTA , . In these complexes, the coordination geometry of the cobalt is octahedral and tetrahedral but no examples of other coordination geometries have been published.…”