The silver(I) coordination polymer [AgO2PPh2]  and unsupported Ag⋯Ag interactions derived from aminophosphinate and phosphinic acid

Moodley, Vashen; Mthethwa, Londiwe; Pillay, Michael N.; Omondi, Bernard; Zyl, Werner E. van

doi:10.1016/j.poly.2015.06.033

Cited by 7 publications

(2 citation statements)

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“…The commercially available diphenylphosphinic acid, Ph 2 P(O)OH, was seen as a pnictogen analogue of benzoic acid that had previously found success in the synthesis of iodine(I) complexes. This precursor was seen as an ideal analogue, especially given that the silver(I) derivative, (Ph 2 P(O)OAg) n (silver(I) diphenylphosphinate), necessary for subsequent iodine(I) complex synthesis had also already been reported 45 . Nonetheless, a higher-yielding procedure for the synthesis of (Ph 2 P(O)OAg) n ( 1 ) was developed, which gave the species in an 82% yield (Supplementary Note 2 ).…”

Section: Resultsmentioning

confidence: 99%

“…Dry CH 2 Cl 2 was obtained by passing deoxygenated solvents through activated alumina columns (MBraun SPS‐800 Series solvent purification system) and stored under argon over 3 Å molecular sieves. The silver(I) precursor, (Ph 2 P(O)OAg) n , was prepared by an alternate procedure than previously described 45 . For structural NMR assignments, 1 H NMR and 1 H– 15 N NMR correlation spectra were recorded on a Bruker Avance III 500 MHz spectrometer in CD 2 Cl 2 .…”

Section: Methodsmentioning

confidence: 99%

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Iodine(I) pnictogenate complexes as Iodination reagents

Mohan,

Rissanen,

Ward

2024

Commun Chem

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Halogen(I) complexes are widely used as halogenation reagents and traditionally feature homoleptic stabilising Lewis bases, though the recent revitalisation of iodine(I) carboxylate chemistry has provided isolable examples of heteroleptic iodine(I) complexes. This work reports iodine(I) pnictogenate complexes stabilised by a Lewis base (L), Ph2P(O)O─I─L, synthesised via cation exchange from the silver(I) precursor, (Ph2P(O)OAg)n. The complexes were characterised in both solution (1H, 1H-15N HMBC, 31P) and the solid state, and supplemented computationally by DFT studies. Interestingly, these iodine(I) pnictogenates demonstrate a range of stabilities, and have been found to excel as iodination reagents in comparison to carbonyl hypoiodites, with comparable reactivity to the eponymous Barluenga’s reagent in the iodination of antipyrine.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Iodine(I) pnictogenate complexes as Iodination reagents

Mohan,

Rissanen,

Ward

2024

Commun Chem

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Metal-binding motifs of alkyl and aryl phosphinates; versatile mono and polynucleating ligands

Carson¹,

Healy²,

Doidge³

et al. 2017

Coordination Chemistry Reviews

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An analysis of 552 structures of metal complexes of alkyl and arylphosphinates in the Cambridge Crystallographic Database shows that the phosphinate ligating group is remarkably versatile and is able to adopt ten different binding motifs in both mono-and polynuclear complexes in which an individual phosphinate group can bind to up to five metal atoms. The majority of both homo-and heteroleptic complexes contain M-O-PR2-O-M units in oligomeric and polymeric structures. In many heteroleptic complexes ligands containing hydrogen bond donors form strong bonding interactions with the phosphinate, generating pseudochelated structures. Similar pseudochelates, − O-PR2=O … H-O-PR2=O, are formed when both a phosphinate and its parent phosphinic acid are coordinated to a single metal atom. Such structures feature also in the solution chemistry involved in metal extraction processes using phosphinate ligands. As might be expected, many of the binding motifs found in phosphinate complexes are similar to those in carboxylate complexes but there are fewer examples of phosphinates being used to form metal organic frameworks.

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