Reactions of Palladium Chloride with Amino Spirocyclic Cyclotriphosphazenes: Isolation and Crystal Structures of Novel Mono- and Bimetallic Complexes Formed by the Hydrolysis of a .lambda.5-Diazaphospholane Ring

Chandrasekaran, A.; Krishnamurthy, S. S.; Nethaji, Munirathinam

doi:10.1021/ic00092a012

Cited by 35 publications

(22 citation statements)

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“…The efficacy of the cyclophosphazene ring as a building block for the construction of multi-site ligand systems is demonstrated by some of the examples [24][25][26][27][28] shown in Scheme 6. Other earlier examples that are known include phosphines, acetylinic moieties, carboranyl derivatives, schiff base linkages etc.…”

Section: Other Types Of Nitrogen Donor Ligands Constructed On Cycloph...mentioning

confidence: 99%

“…27 Mixed amino cyclophosphazenes, particularly those containing a spirocyclic diamino substituent and dimethylamino groups such as the compound 31 have been shown to interact with transition metals. 28 The structures of the palladium complexes have been determined. The coordination to palladium occurs through one of the nitrogen atoms of the diaminoalkane moiety and an adjacent ring nitrogen atom of the phosphazene skeleton as shown for 35.…”

Section: Other Types Of Nitrogen Donor Ligands Constructed On Cycloph...mentioning

confidence: 99%

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Phosphazenes as scaffolds for the construction of multi-site coordination ligands

2001

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Section: Other Types Of Nitrogen Donor Ligands Constructed On Cycloph...mentioning

confidence: 99%

Section: Other Types Of Nitrogen Donor Ligands Constructed On Cycloph...mentioning

confidence: 99%

Phosphazenes as scaffolds for the construction of multi-site coordination ligands

2001

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“…[2,5] It is known that the P 3 N 3 Y 6 molecules (Y = alkoxy, alkyl, NH 2 , NHR, NR 2 , etc.) are versatile ligands for transition metals, for example, P 3 N 3 -(NMe 2 ) 4 (NHCH 2 CH 2 NH)·PdCl 2 , [6] P 3 N 3 (OPh) 4 (Pz) 2 ·PdCl 2 , [6] and P 3 N 3 (OPh) 4 (Pz) 2 ·Mo(CO) 3 [1] (Pz = dimethylpyrazolyl). Some covalently bound complexes in which a transitionmetal fragment substitutes one or two halogen atoms in P 3 N 3 X 6 (X = halogen), are also known, for example, [(CO) 2 CpFe]P 3 N 3 F 4 , [7] N 3 P 3 Cl 5 [Cr(CO) 3 Cp], [8] and N 3 P 3 Cl 4 (Cp)[Mo(CO) 3 Cp].…”

Section: Introductionmentioning

confidence: 99%

“…[26] While P 3 N 3 Me 6 Abstract: The first solid-state structures of complexed P 3 N 3 X 6 (X = halogen) are reported for X = Cl. The compounds were obtained from P 3 N 3 Cl 6 and Ag[Al(OR) 4 ] salts in CH 2 Cl 2 /CS 2 solution. The very weakly coordinating anion with R = C(CF 3 ) 3 led to the salt Ag(P 3 N 3 Cl 6 ) 2 + [Al(OR) 4 ] À (1), but the more strongly coordinating anion with R' = C(CH 3 )(CF 3 ) 2 gave the molecular adduct (P 3 N 3 Cl 6 )AgAl(OR') 4 (3 4 ] À (2), in which Ag + is coordinated by two phosphazene and one CH 2 Cl 2 ligands, were isolated from CH 2 Cl 2 solution.…”

Section: Introductionmentioning

confidence: 99%

Silver Complexes of Cyclic Hexachlorotriphosphazene

Gonsior

Antonijevic

Krossing

2006

Chemistry A European J

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The first solid-state structures of complexed P3N3X6 (X = halogen) are reported for X = Cl. The compounds were obtained from P3N3Cl6 and Ag[Al(OR)4] salts in CH2Cl2/CS2 solution. The very weakly coordinating anion with R = C(CF3)3 led to the salt Ag(P3N3Cl6)2+[Al(OR)4]- (1), but the more strongly coordinating anion with R' = C(CH3)(CF3)2 gave the molecular adduct (P3N3Cl6)AgAl(OR')4 (3). Crystals of [Ag(CH2Cl2)(P3N3Cl6)2]+[Al(OR)4]- (2), in which Ag+ is coordinated by two phosphazene and one CH2Cl2 ligands, were isolated from CH2Cl2 solution. The three compounds were characterized by their X-ray structures, and 1 and 3 also by NMR and vibrational spectroscopy. Solution and solid-state 31P NMR investigations in combination with quantum chemically calculated chemical shifts show that the 31P NMR shifts of free and silver-coordinated P3N3Cl6 differ by less than 3 ppm and indicate a very weakly bound P3N3Cl6 ligand in 1. The experimental silver ion affinity (SIA) of the phosphazene ligand was derived from the solid-state structure of 3. The SIA shows that (PNCl2)3 is only a slightly stronger Lewis base than P4 and CH2Cl2, while other ligands such as S8, P4S3, toluene, and 1,2-Cl2C2H4 are far stronger ligands towards the silver cation. The energetics of the complexes were assessed with inclusion of entropic, thermal, and solvation contributions (MP2/TZVPP, COSMO). The formation of the cations in 1, 2, and 3 was calculated to be exergonic by delta(r)G(degrees)(CH2Cl2) = -97, -107, and -27 kJ mol(-1), respectively. All prepared complexes are thermally stable; formation of P3N3Cl5+ and AgCl was not observed, even at 60 degrees C in an ultrasonic bath. Therefore, the formation of P3N3Cl5+ was investigated by quantum chemical calculations. Other possible reaction pathways that could lead to the successful preparation of P3N3X5+ salts were defined.

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“…The mono and bimetallic complexes 139 and 141 were developed by Chandrasekaran and co‐worker by reactions (Scheme 34) of palladium chloride with amino spirocyclic CTP 138 and 140 , respectively [111] . In the complex 139 , the palladium(II) binds with nitrogen atom of amino‐alkane moiety and ring nitrogen atom of CTP to form the four membered ring with non‐planar geometry at the metal centre.…”

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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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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Reactions of Palladium Chloride with Amino Spirocyclic Cyclotriphosphazenes: Isolation and Crystal Structures of Novel Mono- and Bimetallic Complexes Formed by the Hydrolysis of a .lambda.5-Diazaphospholane Ring

Cited by 35 publications

References 0 publications

Phosphazenes as scaffolds for the construction of multi-site coordination ligands

Phosphazenes as scaffolds for the construction of multi-site coordination ligands

Silver Complexes of Cyclic Hexachlorotriphosphazene

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

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