Structure of the pyridine adduct of dithiophosphoryl monochloride

Averbuch-Pouchot, Μ. Τ.; Meisel, M.

doi:10.1107/s010827018900452x

Cited by 9 publications

(4 citation statements)

References 4 publications

(5 reference statements)

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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: 84%

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: 84%

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

Gudat

2014

Angew Chem Int Ed

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“…The complexes listed in Table can all be considered to involve a coordinate N−P interaction. Complex 4 is formally a pyridine-like ligand on a cationic phosphine (phosphenium) 12 and is a direct analogue of 2b , while 5 , 6 , 7 , and 8 involve phosphorus in a higher formal oxidation state and coordination number. The N−P coordinate bonds are predictably longer in the neutral complexes 1a , 1b , 6 , and 7 than observed for the cations 2b, 3a , 3b , 4 , 5 , and 8 , presumably due to the relatively stabilized acceptor orbital at the phosphorus center in the cations.…”

Section: Resultsmentioning

confidence: 99%

Nitrogen Ligands on Phosphorus(III) Lewis Acceptors: A Versatile New Synthetic Approach to Unusual N−P Structural Arrangements

et al. 2003

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A series of Lewis acid-base adducts of phosphines with amines or pyridines have been prepared and structurally characterized, demonstrating the importance of Lewis acceptor behavior in the chemistry of electron-rich (lone-pair-bearing) centers. The neutral and cationic complexes all contain examples of N-P coordinate bonds that are void of N-P pi-bonding and therefore represent definitive N-P single bonds. The structures are examples of N-P topologies that are rare or have not previously been observed, highlighting the synthetic viability of Lewis acid-base coupling in the still developing field of nitrogen-phosphorus chemistry.

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“…The high electronegativity of F-ligands apparently fully compensates the negative charge of the [PO 2 F 2 ] - ion. The average P−N bond lengths of 1.756 Å ( 1 ·CH 3 CN) and 1.738 Å ( 2 ) are somewhat longer then the single P−N bond in [PO 2 (NH 2 ) 2 ] - (1.678 Å) 29 but significantly shorter than a typical P−N dative bond in the betaine (py)PS 2 Cl (1.849 Å) . This shortening can be attributed to a greater Lewis acidity of [PO 2 ] + with respect to the PS 2 Cl molecule and in part to the overall positive charge of [(DMAP) 2 PO 2 ] + .…”

Section: Resultsmentioning

confidence: 95%

Base-Induced Dismutation of POCl₃ and POBr₃: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations

et al. 2004

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The interaction between POCl(3) or POBr(3) and pyridine or DMAP has been reinvestigated to clarify the discrepancies between previously published results concerning the Lewis acidity of phosphoryl halides and their behavior toward pyridine bases. The obtained results show that POCl(3) virtually does not react with pyridine, while it does with 4-(dimethylamino)pyridine (DMAP), even in SO(2) solution, to yield an ionic compound [(DMAP)(2)PO(2)]Cl.3SO(2) (1.3SO(2)). Its recrystallization from acetonitrile gives [(DMAP)(2)PO(2)]Cl.CH(3)CN (1.CH(3)CN). The POBr(3) reacts readily with both DMAP and pyridine forming the analogous tribromides, [(DMAP)(2)PO(2)]Br(3) (2) and [(py)(2)PO(2)]Br(3) (3), respectively. Treatment of 3 with Me(3)SiOSO(2)CF(3) in acetonitrile solution led to [(py)(2)PO(2)][CF(3)SO(3)].CH(3)CN (4), while the reaction between 1.CH(3)CN and Me(3)SiOPOF(2) gave [(DMAP)(2)PO(2)][PO(2)F(2)] (5). The crystal structures of 1.CH(3)CN, 1.3SO(2), 2, and 4 revealed that all four compounds are ionic containing the distorted tetrahedral cations [(DMAP)(2)PO(2)](+) and [(py)(2)PO(2)](+). Both ions represent a donor-stabilized form of the so far unknown cation [PO(2)](+). The geometry of [(DMAP)(2)PO(2)](+), optimized by density functional calculations at the B3LYP/6-31G(d,p) level, is in good agreement with X-ray structural data. The NBO analysis of natural atomic charges shows an extensive delocalization of the [PO(2)](+) intrinsic positive charge and indicates a contribution of the electrostatic attraction to the formation of N-P donor-acceptor bonds. According to a (31)P NMR study, the reactions of both phosphoryl halides with DMAP proceed via successive formation of the intermediates [(DMAP)POX(2)](+) and (DMAP)PO(2)X to give an equimolar mixture of [(DMAP)(2)PO(2)](+) and PX(5) (X = Cl, Br) as the end products. The NMR spectroscopic identification of the cations [(DMAP)POX(2)](+) and [(DMAP)(2)PO(2)](+) was supported by ab initio calculations of their chemical shifts.

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Structure of the pyridine adduct of dithiophosphoryl monochloride

Cited by 9 publications

References 4 publications

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

Nitrogen Ligands on Phosphorus(III) Lewis Acceptors: A Versatile New Synthetic Approach to Unusual N−P Structural Arrangements

Base-Induced Dismutation of POCl₃ and POBr₃: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations

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Structure of the pyridine adduct of dithiophosphoryl monochloride

Cited by 9 publications

References 4 publications

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

New Phosphorus Analogues of Nitrogen Classics—No Carbon Copies

Nitrogen Ligands on Phosphorus(III) Lewis Acceptors: A Versatile New Synthetic Approach to Unusual N−P Structural Arrangements

Base-Induced Dismutation of POCl3 and POBr3: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations

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Base-Induced Dismutation of POCl₃ and POBr₃: Synthesis and Structure of Ligand-Stabilized Dioxophosphonium Cations