Diamidonaphthalene-Stabilized N-Heterocyclic Pnictogenium Cations and Their Cation−Cation Solid-State Interactions

Spinney, Heather A.; Korobkov, Ilia; DiLabio, Gino A.; Yap, and Glen P. A.; Richeson, Darrin S.

doi:10.1021/om7004436

Cited by 38 publications

(42 citation statements)

References 34 publications

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“…Single-crystal X-ray structural studies on the 1,8-diamidonaphthalene-derived cyclic chlorophosphines 32 (Scheme 18 ) [92,93] revealed the presence of sixmembered heterocyclic rings with superficially similar conformations as observed for P-halogen-diketiminato-phosphenium ions and likewise rather short (2.15-2.17 Å) P-Cl bonds. The pyramidal coordination geometry of the phosphorus atoms and the P-N bond lengths (1.67-1.68 Å) match the appropriate parameters for five-membered ring NHPs.…”

Section: Physical Properties Structure and Bondingmentioning

confidence: 94%

“…The pyramidal coordination geometry of the phosphorus atoms and the P-N bond lengths (1.67-1.68 Å) match the appropriate parameters for five-membered ring NHPs. In contrast, the cations of the salts 33 (Scheme 18 ) obtained after chloride abstraction are distinguished by nearly planar six-membered rings with distinctly shorter P-N bonds (1.61-1.63 Å) [92,93] . Interestingly, the C-N bond distances in the six-membered rings remain similar in both cations and neutral chlorophosphines.…”

Section: Physical Properties Structure and Bondingmentioning

confidence: 98%

“…Heterocyclic phosphines 32 were prepared from base-induced condensation of a secondary 1,8-diamino-naphthalene with phosphorus trichloride (the corresponding As-and Sb-analogues were obtained analogously) and converted into cyclic phosphenium cations 33 by Lewis acid promoted halide abstraction using GaCl 3 or trimethylsilyl triflate as reagents (Scheme 18 ) [15,92] . …”

Section: Synthesesmentioning

confidence: 99%

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Recent Developments in the Chemistry of N-Heterocyclic Phosphines

Gudat

2009

Topics in Heterocyclic Chemistry

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This chapter gives a survey on five-and six-membered phosphorusnitrogen heterocyclic compounds whose rings combine a phosphazene (>N-P = N-) or phosphazane (>N-P(X)-N<) unit with an unsaturated C 2 or C 3 building block. Representatives contain structurally diverse species like aromatic 1,3,2-diazaphosphinines and (benzo)-1,3,2-diazaphospholes, cationic counterparts of subvalent main-group carbene analogues like 1,3,2-diazaphospholenium ions and phosphenium-diketiminates, and neutral heterocycles like 1,3,2-diazaphospholenes featuring unusual structures and reactivities. The exploration of these species developed rapidly in the last two decades in the wake of cutting edge research on multiple bonding and low coordination in the chemistry of heavier main-group elements, and the discovery of stable carbenes. This review summarizes the elaboration of synthetic approaches for different types of N -heterocyclic phosphine derivatives, discusses their characterization by physical and computational methods which furnished a thorough understanding of structure and bonding, and finally highlights accomplishments in the exploration of the chemical properties at the border of classical organic heterocyclic chemistry and molecular inorganic chemistry.

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Section: Physical Properties Structure and Bondingmentioning

confidence: 94%

Section: Physical Properties Structure and Bondingmentioning

confidence: 98%

Section: Synthesesmentioning

confidence: 99%

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Recent Developments in the Chemistry of N-Heterocyclic Phosphines

Gudat

2009

Topics in Heterocyclic Chemistry

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“…[18] Only little is known about compounds with dicoordinated Sb atoms containing a Sb À N double bond. [26,27] The first fully characterized compound with a partial SbÀN double bond (1.99(2) and 2.00 (2) [26a]…”

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An Unusual Isomerization to Tetraazastiboles

2011

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Dedicated to Professor Peter Klüfers on the occasion of his 60th birthdayPentazoles are aromatic molecules consisting of a fivemembered nitrogen-atom ring (Scheme 1), one of which is bonded to a hydrogen atom (HN 5 ) or an organic substituent (RN 5 ; R is usually an aryl group). They form a class of highly endothermic and explosive compounds. The existence of an all-nitrogen aromatic azole ring, RN 5 (R = C 6 H 5 ), was considered by Clusius and Hurzeler [1] and shown by Huisgen and Ugi [2] in the reaction of phenyldiazonium chloride, [C 6 Substitution of one nitrogen atom in pentazoles by a heavier element of Group 15 leads to isovalent tetraazapnictoles (Scheme 1), RN 4 E (E = P, As, Sb, Bi), which also have electronic structures that are related to those of aromatic hydrocarbons with (4n + 2)p electrons.[3] Only recently, two examples of tetraazapnictoles (E = P, R = Mes* = 2,4,6-tritert-butylphenyl or m-Ter = 2,6-bis(2,4,6-trimethylphenyl)-phenyl;[4a, 5] E = As, [6] R = Mes*) have been isolated and fully characterized. Two different synthetic routes to tetraazapnictoles have been described: [4,6]

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“…Similar to phosphenium ions, amino group(s) directly attached to arsenic or antimony provide stabilization through strong electron donation(308)(309)(310)(311) 729,[753][754][755][756][757]. The As and Sb analogs of 289 and 290 have also been prepared and characterized 734,735. The As and Sb analogs of 289 and 290 have also been prepared and characterized 734,735.…”

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confidence: 99%