A Novel Cyclotriphosphazene Complex with a Short Transannular P...P Contact

Thomas, K. R. Justin

doi:10.1107/s0108270197015114

Cited by 3 publications

(5 citation statements)

References 3 publications

(3 reference statements)

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“…The coordination mode of the ligand in complexes 121 and 122 is found to be κ 3 N non‐geminal coordination with geometry of distorted trigonal bipyramidal matches as similar to complex 117 . Likewise, the analogous cobalt (II) complexes 123 – 126 have been synthesised by reaction (Scheme 31) of CoCl 2 with ligands 27 , 31 , 37 and 38 , respectively [101–104] . Also, the geometry as well as coordination modes of 123 – 126 are being noticed as similar to that of complex 117 .…”

Section: Metal Clusters By Exocyclic Ligand Sites and Skeletal Ring Nmentioning

confidence: 97%

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Multisite Coordination Ligands on Cyclotriphosphazene Core for the Assembly of Metal Clusters and Porous Coordination Polymers

et al. 2021

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In this review, we account the recent advancements on cyclotriphosphazene (N3P3Cl6) based multi‐site coordination ligands for the synthesis of multi‐metallic architectures. In case of N3P3Cl6, Phosphorous centres with two chlorides use to be bonded with nitrogen [−P(Cl2)=N−]3 at alternative positions in six membered ring to provide a robust planar structure to anchor the ligand arms with wide flexibility. Cyclic P−N robust motif is renowned as the potential support for the design of multi‐site ligands originating from phosphorus centres by viable substitution of variable number of ligand units (1 to 6) consist of one or more coordination site(s) via geminal and/or non‐geminal modes. Despite these phosphorus centres are promising to support in ligand structure, occasionally involve in coordination with transition metals as well. Three of alternative nitrogen atoms in this heterocyclic core are supposed to function as Lewis base centres while the electron releasing substituents occurred to tether on phosphorus centres, also when the resultant ring size favours adequate interaction towards the transition metal ions with respect to skeletal flexibility. The ligand modes vary with respect to numbers and orientation of coordination sites, which is imperative to enrich the ligation ability. Moreover, several examples of cyclotriphosphazene core ligands consist of the spacer oxygen atom while tethering with exocyclic ligand units to incorporate more flexibility. In accordance with coordination sites on ligand framework and choice of metal, the skeletal ring nitrogen atom(s) of the cyclotriphosphazene can be involved in coordination with metal ions. Indeed, the coordination of ligands is reported to coordinate with main group, transition and lanthanide metal ions to form variety of metal clusters and porous coordination polymers. Subsequently, the geometry of homo or heterometallic complexes with respect to versatile coordination modes of metallic complexes tends to afford inherent chemical properties for specific application. In terms of exocyclic ligands, the heterocyclic units such as pyridyloxy‐, pyrazolyl‐, pyridylalkylamino‐, bipyridyl‐, 1,10‐phenanthroline, porphyrinato, hydrazide, hydrazone, Schiff's base and spirocyclic amine units attached to cyclotriphosphazene were exploited to form series of metal complexes. Similarly, the variety of metal clusters, polymeric network (1D to 3D) and porous coordination polymers have been reported on basis of cyclic core molecule substituted with ligand units, pyridyloxy‐, multi‐carboxylic, aromatic amines substituted pyridyloxy‐ and imidazole moiety involved to form variety of products.

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Section: Metal Clusters By Exocyclic Ligand Sites and Skeletal Ring Nmentioning

confidence: 97%

“…In 1990s, V. Chandrashekar and co‐workers have intensely studied the coordination chemistry of diverse pyrazolylCTP ligands ( 26 , 27 , 31 , 37 and 38 ) with series of transition metals upon synthesis of novel pyrazolylCTP metal complexes 117 – 125 [54,55,98–104] …”

Section: Metal Clusters By Exocyclic Ligand Sites and Skeletal Ring Nmentioning

confidence: 99%

Multisite Coordination Ligands on Cyclotriphosphazene Core for the Assembly of Metal Clusters and Porous Coordination Polymers

et al. 2021

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“…X-ray characterization of compounds 111 [143] and 112 [144] confirm that the structures are racemic analogous to the non-metallo 1,3-transdisubstituted cyclophosphazene derivatives (Section 4.2). The majority of the metallo-cyclophosphazene derivatives with centers of chirality have two equivalent centers corresponding to the 1,3-cis-disubstituted meso form and some examples have been given below (113 [145], 114 [146], 115 [147], 116 [73], 117a [148], 117b [149], 117c [150], 118 [151], 119a [86],119b [34h], 120a [152], 120b [153], 121a,b [154] and 122 [155]). Compound 123 [156] which has a pseudoasymmetric center is a meso form.…”

Section: Application To Metallo-cyclophosphazenesmentioning

confidence: 99%

“…37.76 kcal/mol) so both R-and S-forms are stable at room temperature and the two enantiomers are commercially available as well as the racemate. Chiral spirophosphazenes containing BN groups can be obtained by the reaction of trimer, N 3 P 3 Cl 6 , with the appropriate number of equivalents of BN (R/S, R or S) to give mono- (148), di- (149) or tri-spiro (150) derivatives as reported by several research groups [178][179][180][181][182][183] and summarized in Fig. 29.…”

Section: Binaphthoxy (Bn) Derivativesmentioning

confidence: 99%

Chiral configurations in cyclophosphazene chemistry

Uslu

Yeşilot

2015

Coordination Chemistry Reviews

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“…Irrespective of whether the ligand contains four or six 3,5-dimethylpyrazolyl groups, for Co(), Ni(), Cu(/), Zn(), Cd() and Hg(), predominantly κ 3 N tridentate binding (involving one phosphazene ring nitrogen atom) is observed. [2][3][4][5][6][7][8][9] In contrast, hexakis(2-pyridyloxy)cyclotriphosphazene (L) is capable of forming uni-, bi-, tri-, tetra-and penta-dentate complexes with first-row transition metal halides. 10 We report here on its reaction with CuCl 2 , to yield a dimeric phosphazene-metal complex where each subunit features an uncoordinated pyridyloxy group, thereby offering the potential for higher order oligomerisation.…”

mentioning

confidence: 99%