Cyclic phosphenium and arsenium cations with 6π electrons and related systems

Carmalt, Claire J.; Lomeli, Viviana

doi:10.1039/a704838f

Cited by 107 publications

(75 citation statements)

References 14 publications

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“…Especially heterocyclic derivatives with boron (B), [3] gallium (C and D), [4] silicon (E), [5] germanium (F), [6] tin (G), [7] phosphorus (H), [8] arsenic (I), [8] antimony (J), [9] and selenium (K) [10] have been reported (Scheme 1). Moreover, the β-diketiminato ligands proved to be very effective ligands for elements of group 13.…”

Section: Introductionmentioning

confidence: 99%

Monomeric Boron and Tin(II) Heterocyclic Derivatives of 1,8‐Diaminonaphthalenes: Synthesis, Characterization and X‐ray Structures

et al. 2008

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The reaction of the diaminonaphthalene dilithium salt (THF) 2 Li 2 [(NSiMe 3 ) 2 C 10 H 6 ] with BX 3 (X = Cl, Br) in hexane provides the monomeric compounds BX[(NSiMe 3 ) 2 C 10 H 6 ] [3 (X = Cl), 4 (X = Br)] with a tricoordinate boron atom. Attempts to reduce 3 and 4 with lithium, sodium, potassium or sodium/ potassium alloy with the intention to isolate a boranide resembling a carbene were unsuccessful. However, the diaminonaphthalene dilithium salt (THF) 2 Li 2 [(NSi-iPr 3 ) 2 C 10 H 6 ] (2) reacts with SnCl 2 in THF to provide the carbene analog 5. Compounds 2, 3 and 5 were characterized by single-crystal

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Section: Introductionmentioning

confidence: 99%

Monomeric Boron and Tin(II) Heterocyclic Derivatives of 1,8‐Diaminonaphthalenes: Synthesis, Characterization and X‐ray Structures

et al. 2008

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“…28,[73][74][75][76][77] One major difference between these two species is the additional stabilization gained from the delocalization of a 6π-electron system in the case of the fivemembered ring, contrary to the 4π-electrons present in the four-membered ring. While aromaticity is not a necessity for the isolation of NHPs 25,34,35,37,38,67 and has been found to be a weak factor in their stabilization, 75 the lack thereof in our four-membered diaminochlorophosphines may be a contributing factor to the difficulty in halide abstraction.…”

Section: Otf = [F3cso3]¯)mentioning

confidence: 99%

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

et al. 2012

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The reported chemistry and reactivity of guanidinate supported group 15 elements in the +3 oxidation state, particularly phosphorus, is limited when compared to their ubiquity in supporting metallic elements across the periodic table. We have synthesized a series of chlorophosphines utilizing homo-and heteroleptic (dianionic)guanidinates and have completed a comprehensive study of their reactivity. Most notable is the reluctancy of these four-membered rings to form the corresponding Nheterocyclic phosphenium cations, the tendency to chemically and thermally eliminate carbodiimide and the scarcely observed ring expansion by insertion of a chloro(imino)phosphine into a P-N bond of the P-N-C-N framework.Computational analysis has provided corroborating evidence for the unwillingness of the halide abstraction reaction by demonstrating the exceptional electron acceptor properties of the target phosphenium cations and the underscoring strength of the P-X bond.

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“…Five-membered phosphorus-nitrogen heterocycles like 1,3,2-diazaphospholidines 1 1 and 1,3,2-diazaphospholenes 2 2,3,4 (Scheme 1) are of central importance for the synthesis of stable phosphenium ions 3, 4 with a cationic, two-coordinate phosphorus atom 5,6,7 which are isoelectronic analogues to neutral diaminocarbenes 5, 6, respectively. Whereas cations 3 with CC-saturated heterocyclic rings were among the first phosphenium ions ever prepared,…”

Section: Introductionmentioning

confidence: 99%

“…under heterolytic cleavage of the phosphorus-chlorine bonds. 5,6,7 Cations 4 have alternatively been accessed via a [1+4]-cycloaddition route starting from a diazabutadiene and a transient P(I) fragment generated via disproportionation of PI 3 , or via reduction of PCl 3 with SnCl 2 , respectively. 10 In view of this approach we became interested in the synthesis of derivatives 7 featuring both a five-membered phosphorus-nitrogen heterocycle and a diazabutadiene moiety.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and characterization of a 2-chloro-1,3,2-diaza-phospholidine-4,5-diimine

Mourgas¹,

Benkő²,

Förster³

et al. 2012

Arkivoc

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An oxalamidine 10a was used as precursor for the synthesis of 2-chloro-1,3,2-diazaphospholidine-4,5-diimine 7a. Both products were characterized by single-crystal X-ray diffraction studies which revealed for 7a the presence of an unusually short P-Cl bond distance. In contrast to other known 2-chloro-1,3,2-diazaphospholidines, 7a fails to react with gallium trichloride, trimethylsilyl trilate, or silver triflate via heterolytic P-Cl bond fission and formation of an N-heterocyclic phosphenium ion. A computational study suggests that this unusual behavior is due to the fact that the exocyclic imino-groups stabilize the P-Cl bond in 7a by diminishing the hyperconjugation between the lone-pairs of the ring nitrogen atoms and the σ*(P-Cl) orbital and destabilize at the same time the hypothetical phosphenium cation.

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Cyclic phosphenium and arsenium cations with 6π electrons and related systems

Cited by 107 publications

References 14 publications

Monomeric Boron and Tin(II) Heterocyclic Derivatives of 1,8‐Diaminonaphthalenes: Synthesis, Characterization and X‐ray Structures

Monomeric Boron and Tin(II) Heterocyclic Derivatives of 1,8‐Diaminonaphthalenes: Synthesis, Characterization and X‐ray Structures

Synthesis, Reactivity, and Computational Analysis of Halophosphines Supported by Dianionic Guanidinate Ligands

Synthesis and characterization of a 2-chloro-1,3,2-diaza-phospholidine-4,5-diimine

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