Kinetically Controlled Protonation of a Cyclic Phosphamethanide Complex to a PH-Phosphonium Ylide

Ekici, Sahir; Gudat, Dietrich; Nieger, Martin; Nyulászi, László; Niecke, Edgar

doi:10.1002/1521-3773(20020916)41:18<3367::aid-anie3367>3.0.co;2-7

Cited by 21 publications

(11 citation statements)

References 7 publications

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“…The most closely related systems to compound 1 are the bis‐iminopyridine analogue 2,6‐bis(2‐phosphaethenyl)pyridine (Figure 2, III) , first reported by Geoffroy et al 11. and bis‐phosphaalkene‐pyridines of type IV (Figure 2) described by Nieke and co‐workers 12…”

Section: Methodsmentioning

confidence: 77%

Diphosphinine Derivatives of Terpyridine: A New Class of Neutral π‐Accepting PNP‐Pincer Ligands

Müller

Pidko

Lutz

et al. 2008

Chemistry A European J

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The first diphosphinine analogue of terpyridine has been developed, which represents a new class of π‐accepting neutral PNP‐pincer ligands. Its electronic properties were evaluated by means of DFT calculations and the corresponding CuIBr complex was characterized crystallographically. The molecular structure revealed a distorted tetrahedral coordination geometry of the CuI center, due to an unusual coordination mode of the two phosphinine ligands (see graphic).

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Section: Methodsmentioning

confidence: 77%

Diphosphinine Derivatives of Terpyridine: A New Class of Neutral π‐Accepting PNP‐Pincer Ligands

Müller

Pidko

Lutz

et al. 2008

Chemistry A European J

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“…This is in accordance with the general understanding 137 that in the condensed phase H-ylides of phosphorus (F) rearrange to their phosphane (A) counterparts via 1,2-H-shift 138 with the exception of some notable kinetically hindered cases. 139,140 In case of 1, 2, 7, and 8, no F-type structure could be optimized (neither at ω-B97XD/cc-pVTZ nor at M06-2X/cc-pVTZ see Tables 1 and S4), only very weakly bonded complexes with P−C distance over 3.2 Å could be obtained. Furthermore, among the F-type PH 3 adducts, only the least stabilized carbenes (ΔE ISO < ca.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Stretching the P–C Bond. Variations on Carbenes and Phosphanes

2020

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The stability and the structure of adducts formed between four substituted phosphanes (PX3, X:H, F, Cl, and NMe2) and 11 different carbenes have been investigated by DFT calculations. In most cases, the structure of the adducts depends strongly on the stability of the carbene itself, exhibiting a linear correlation with the increasing dissociation energy of the adduct. Carbenes of low stability form phosphorus ylides (F), which can be described as phosphane → carbene adducts supported with some back-bonding. The most stable carbenes, which have high energy lone pair, do not form stable F-type structures but carbene → phosphane adducts (E-type structure), utilizing the low-lying lowest unoccupied molecular orbital (LUMO) of the phosphane (with electronegative substituents), benefiting also from the carbene–pnictogen interaction. Especially noteworthy is the case of PCl3, which has an extremely low energy LUMO in its T-shaped form. Although this PCl3 structure is a transition state of rather high energy, the large stabilization energy of the complex makes this carbene–phosphane adduct stable. Most interestingly, in case of carbenes with medium stability both F- and E-type structures could be optimized, giving rise to bond-stretch isomerism. Likewise, for phosphorus ylides (F), the stability of the adducts G formed from carbenes with hypovalent phosphorus (PXphosphinidene) is in a linear relationship with the stabilization of the carbene. Adducts of carbenes with hypervalent phosphorus (PX5) are the most stable when X is electronegative, and the carbene is highly nucleophilic.

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“…Pincer ligands with a PNP-set of donor centers connected by a central pyridine ring have become a common structural motif for the synthesis of a variety of metal complexes [1–15] . Especially for pincers of this type in which the phosphorus atoms are part of a P C double bond, conjugation of the pendant unsaturated units with the central pyridine ring has to be considered [3,8,14] .…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structure and π-delocalization of a phosphaalkenyl based neutral PNP-pincer

Orthaber¹,

Belaj²,

Pietschnig³

2011

Inorganica Chimica Acta

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Graphical abstractA novel bis-phosphaalkenyl based PNP-pincer was prepared and its crystal structure indicates delocalization over the entire π-system including all three donor sites which is also supported by spectroscopic measurements and DFT calculations. The coordination chemistry of the pincer and its precursor have been explored using Cu(I).Highlights► A novel bis-phosphaalkenyl based PNP-pincer was prepared. ► The crystal structure indicates delocalization over the entire π-system including all three donor sites. ► DFT calculations and UV–Vis measurements support the interpretation of the structural findings. ► The coordination behavior towards Cu(I) is explored on a preliminary base.

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Kinetically Controlled Protonation of a Cyclic Phosphamethanide Complex to a PH-Phosphonium Ylide

Cited by 21 publications

References 7 publications

Diphosphinine Derivatives of Terpyridine: A New Class of Neutral π‐Accepting PNP‐Pincer Ligands

Diphosphinine Derivatives of Terpyridine: A New Class of Neutral π‐Accepting PNP‐Pincer Ligands

Stretching the P–C Bond. Variations on Carbenes and Phosphanes

Synthesis, structure and π-delocalization of a phosphaalkenyl based neutral PNP-pincer

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