Reactions of aminophosphines with carbon dioxide, carbonyl sulfide, and carbon disulfide. Crystal and molecular structure of a seven-coordinate tris(dithiocarbamato) complex of phosphorus(III)

Light, R. W.; Hutchins, L. D.; Paine, Robert T.; Campana, Charles F.

doi:10.1021/ic50214a008

Cited by 44 publications

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“…The true nature of the structures as pseudo-seven coordinate derivatives of P(III) was revealed only by the X-ray crystal structural analysis of P(S 2 CNMe 2 ) 3 (85) in 1980 by Paine and co-workers (Table 14). 137 The high-field 31 P NMR chemical shift value observed (-62.6 ppm) is consistent with a significant increase of coordination number relative to that of tricoordinate phosphines. The structure of 85 ( Figure 45) can be described as a PS 6 polyhedron which has a geometry approximating a distorted trigonal antiprism or a distorted capped octahedron.…”

Section: Pseudo-seven-coordinate Phosphorus(iii)supporting

confidence: 65%

Neutral Six-Coordinate Phosphorus

1996

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Section: Pseudo-seven-coordinate Phosphorus(iii)supporting

confidence: 65%

Neutral Six-Coordinate Phosphorus

1996

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“…The formulation of 8 was also confirmed by its X-ray structure (Figure 3), [12] which showed the pseudo-C 2 -symmetric geometry of the dicarbamatophosphorane, wherein oxygen donors occupy both axial positions, while the C ipso atoms of the aryl groups lie in the equatorial plane. The lengths of mutually trans PÀO bonds were found to be 1.7635 (8) and 1.7773(8) , with an OÀPÀO angle of 174.27(4)8.…”

Section: Methodsmentioning

confidence: 76%

“…The X-ray structure of 3 confirmed this formulation, demonstrating a distorted trigonal bipyramidal geometry at P, which is contained within a strained four-membered ring ( Figure 1). [12] Insertion of CO 2 into the activated P À N bond of 3 results in a six-membered ring with an elongated PÀO bond (1.775(1) and 1.778(1) ) in each of two molecules in the asymmetric unit. The PÀN bond was found to be exceptionally long (1.842 (7) and 1.839(6) ) [13] within each of two crystallographically independent molecules.…”

mentioning

confidence: 99%

“…The X-ray structure of 3 confirmed this formulation, demonstrating a distorted trigonal bipyramidal geometry at P, which is contained within a strained four-membered ring (Figure 1). [12] Although rare (a few amidofluorophosphoranes have previously been prepared), [13] compound 3 is the first to be crystallographically characterized. The PÀN bond was found to be exceptionally long (1.842 (7) and 1.839(6) ) [13] within each of two crystallographically independent molecules.…”

mentioning

confidence: 99%

“…Collectively, these data suggest that 4 is the carbamatofluorophosphorane Ph 2 PF(o-C 6 H 4 N(Me)CO 2 ), and this formulation was confirmed by Xray crystallography (Figure 2). [12] Insertion of CO 2 into the activated P À N bond of 3 results in a six-membered ring with an elongated PÀO bond (1.775(1) and 1.778(1) ) in each of two molecules in the asymmetric unit. Within 4, the geometry about P is trigonal bipyramidal with the carbamato O occupying an axial position trans to F. The C À O and C = O bonds in the CO 2 fragment of 4 average 1.330(2) and 1.212(2) , respectively, which are slightly longer than those seen in tBu 3 PCO 2 B(C 6 F 5 ) 3 (1.299(2) , 1.208(2) ) and…”

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confidence: 99%

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Phosphorus as a Lewis Acid: CO₂ Sequestration with Amidophosphoranes

2012

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The role of CO 2 as a greenhouse gas has prompted widespread efforts for carbon capture. To date, a number of strategies have been developed to sequester this gas using materials such as alumina, silica, zeolites, activated carbon, and metal-organic frameworks (MOFs). [1] While some of these systems are being applied on increasing scale, efforts to discover fundamentally unique strategies for CO 2 capture continue. In this regard, the use of metal-free, frustrated Lewis pairs (FLPs) has received recent attention. [2] In 2009, we reported the reversible binding of CO 2 by borane/ phosphine-based FLPs. [3] Subsequent work by the groups of OHare [4] and Piers, [5] as well as ourselves, [6] has demonstrated the use of B/P, B/N, and Al/P-based FLPs for the conversion of CO 2 into methanol, methane, or CO.While Group 13/15 Lewis acid/base combinations continue to reveal new aspects of FLP chemistry, less attention has been paid to expanding the variety of FLP systems available. A creative departure from the original systems has been described by Alcarazo and co-workers. [7] In that work, all-carbon-based FLPs of N-heterocyclic carbenes and Lewis acidic allenes were described. Another alternative has been developed by Wass and co-workers, [8] who exploited Group 4 metal Lewis acids with bulky phosphines to activate a variety of small molecules. While considering new approaches, we noted the innovative examples of organic transformations and anion capture that are facilitated by Lewis acidic phosphonium cations [9] and queried the viability of such species in FLP chemistry. Herein, we describe the syntheses of aminophosphonium salts, which incorporate Lewis basic and acidic pnictogen functionalities within an intramolecular system. These species serve as hypothetical intermediates for the generation of ring-strained amidophosphoranes, which are shown to sequester CO 2 .Reaction of the o-phosphinoaniline Ph 2 P(o-C 6 H 4 NHMe) [10] with XeF 2[11] at À35 8C in CH 2 Cl 2 produces the off-white difluorophosphorane, Ph 2 PF 2 (o-C 6 H 4 NHMe), 1 (Scheme 1). The 31 P{ 1 H} NMR spectrum of 1 reveals a highfield triplet at d = À45.6 ppm ( 1 J PF = 625 Hz), while the 1 H NMR spectrum depicts the NH resonance as a broad quartet at d = 4.68 ppm ( 3 J HH = 5.0 Hz) that couples to the N-methyl signal at d = 2.67 ppm. With the amine functionality unaffected by fluorination, facile F À abstraction from 1 by Me 3 SiO 3 SCF 3 yields [Ph 2 PF(o-C 6 H 4 NHMe)][O 3 SCF 3 ] (2), a rare example of a compound containing both acidic phosphonium and pendant amine functionalities. The 31 P{ 1 H} NMR spectrum of 2 reveals a strongly deshielded P nucleus with a doublet resonance at d = 94.4 ( 1 J PF = 980 Hz), while the 1 H spectrum is largely unchanged, except for a downfield shift of the NH signal to d = 5.20.The combination of unquenched Lewis acidic and basic pnictogens within 2 prompted our investigation of its potential behavior as an FLP in reactions with CO 2 . Exposure of 2 to an overpressure of 13 CO 2 in CD 2 Cl 2 resulted in no react...

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