Tetrakis(trimethysilyl)hypophosphate P2O2(OTMS)4: Synthesis, reactivity and application as flame retardant

Ruflin, Catherine; Fischbach, Urs; Levalois-Grützmacher, Joëlle

doi:10.1002/hc.20373

Cited by 18 publications

(9 citation statements)

References 22 publications

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“…4 ′) canonical structures. This representation of 4 as a hybrid between a Lewis base complex of P 2 O 4 and a zwitterionic hypophosphonate is in line with the similarity of the bond lengths in the P 2 O 4 units of 4 and a structurally characterized hypophosphate salt with the anion [(RO)O 2 P‐PO 2 (OR)] 2− (R=SiMe 3 ),10 as well as with the reported description of pyridine adducts of dithiophosphoryl chloride, (py)(Cl)PS 2 ,11 and some phosphinates featuring isolated, carbene‐substituted RPO 2 fragments 12. In accord with the generally superior thermal stability of PP over NN single bonds, the fragmentation of 4 into two molecules of ( NHC )PO 2 ( NHC =N‐heterocyclic carbene) that mimics the easily occurring cleavage of N 2 O 4 was not observed.…”

Section: Methodssupporting

confidence: 74%

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

Gudat

2014

Angew Chem Int Ed

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Getting heavy: The recently prepared phosphorus analogues of two old acquaintances, urea and dinitrogen tetroxide, bear some structural resemblance to their archetypes but are no carbon copies. Their syntheses and chemical properties reveal rather certain peculiarities, which back the doctrine that the electronic properties of the heavier elements in a group differ from those of the lightest congener.

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Section: Methodssupporting

confidence: 74%

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

Gudat

2014

Angew Chem Int Ed

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“…In the case of organic derivatives of hypodiphosphoric acid, from a structural point of view, there is a knowledge gap compared to the inorganic derivatives. In the Cambridge Structural Database (CSD, Version 5.38;Groom et al, 2016), there are only two records: the first (without atomic coordinates) is for cyclic tetraalkyl hypodiphosphate (CSD refcode MXPHOS; Gałdecki & Karolak-Wojciechowska, 1971) and the second is for the crystal structure of the bis(trimethylsilyl)hypodiphosphate anion (CSD refcode GINSOM; Ruflin et al, 2007). Considering the structural similarity of the hypodiphosphate skeleton to the naturally occurring diphosphate (pyrophosphate, P V -O-P V ) unit, it seems essential to structurally characterize new analogues of nucleotides with a P IV -P IV bond.…”

Section: Introductionmentioning

confidence: 99%

Adenosine hypodiphosphate ester, an analogue of ADP: analysis of the adenine–hypodiphosphate interaction mode in hypodiphosphate nucleotides and adenine salts

et al. 2018

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Adenosine diphosphate (ADP) plays a crucial role in cell biochemistry, especially in metabolic pathways and energy storage. ADP itself, as well as many of its analogues, such as adenosine hypodiphosphate (AhDP), has been studied extensively, in particular in terms of enzymatic activity. However, structural studies in the solid state, especially for AhDP, are still missing. An analogue of ADP, i.e. adenosine hypodiphosphate ester, has been synthesized and characterized in the crystalline form as two hydrated sodium salts of 2':3'-isopropylideneadenosine 5'-hypodiphosphate (HAhDP, CHNOP for the neutral form), namely pentasodium tetrakis(2':3'-isopropylideneadenosine 5'-hypodiphosphate) tetracosahydrate, 5Na·3CHNOP·CHNOP·24HO or Na(HAhDP)(HAhDP)·24HO, (I), and sodium tetrakis(2':3'-isopropylideneadenosine 5'-hypodiphosphate) pentadecahydrate, Na·CHNOP·2CHNOP·CHNOP·15HO or Na(HAhDP)(HAhDP)(HAhDP)·15HO, (II). Crystal structure analyses of (I) and (II) reveal two nucleoside hypodiphosphate ions in the asymmetric units with different ionization states of the hypodiphosphate unit and adenine base. For all AhDP nucleotides, the same anti conformation about the N-glycosidic bond and similar puckering of the ribose ring have been found. AhDP geometry and interactions have been compared to ADP nucleotides deposited in the Cambridge Structural Database. The adenine-hypodiphosphate interactions, identified as defining nucleotide self-assembly, have been analysed in model systems, i.e. the adenine (Ade) salts of hypodiphosphoric acid, namely bis(adeninium) hypodiphosphate dihydrate, 2CHN·HPO·2HO or (AdeH)(HPO)·2HO, (III), and bis(adeninium) hypodiphosphate, 2CHN·HPO or (AdeH)(HPO), (IV).

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“…In the presence of excess bromotrimethylsilane, (EtO) 2 P(O)NH(O)P(OEt) 2 3 could then be converted into its silyl ester derivative 4 via silylation reaction. Similar to the generation of tetrakis(trimethylsilyl) hypophosphate species, this step is also analogous to the facile dealkylation of phosphonic acid dialkyl ester depicted by McKenna et al …”

Section: Resultsmentioning

confidence: 90%

Ethyl ester and silyl ester of imidodiphosphate: An alternative route to access phosphorus‐nitrogen‐phosphorus bonds via Staudinger reaction

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Levalois-Grützmacher

2018

Heteroatom Chemistry

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We present herein an alternative synthesis route to obtain tetraethyl imidodiphosphate (EtO) 2 P(O)NH(O)P(OEt) 2 (3) and its silylester derivative tetrakis(trimethylsilyl) imidodiphosphate (Me 3 SiO) 2 P(O)NH(O)P(OSiMe 3 ) 2 (4) involving a phosphorazidate intermediate (1) and the Staudinger reaction. Compared to previous methods, this synthesis route is simpler, more atom efficient, and energetically inexpensive.Moreover, the final compounds are obtained with larger yield and higher purity.

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Tetrakis(trimethysilyl)hypophosphate P₂O₂(OTMS)₄: Synthesis, reactivity and application as flame retardant

Cited by 18 publications

References 22 publications

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

Adenosine hypodiphosphate ester, an analogue of ADP: analysis of the adenine–hypodiphosphate interaction mode in hypodiphosphate nucleotides and adenine salts

Ethyl ester and silyl ester of imidodiphosphate: An alternative route to access phosphorus‐nitrogen‐phosphorus bonds via Staudinger reaction

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