Hypervalent Molecules

doi:10.1002/9781118558409.ch14

Orbital Interactions in Chemistry 2013

DOI: 10.1002/9781118558409.ch14

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Hypervalent Molecules

Abstract: Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your si… Show more

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Cited by 4 publications

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Long‐Range Forces in Rock‐Salt‐Type Tellurides and How they Mirror the Underlying Chemical Bonding

et al. 2021

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Chemical bonding in main‐group IV chalcogenides is an intensely discussed topic, easily understandable because of their remarkable physical properties that predestine these solid‐state materials for their widespread use in, for instance, thermoelectrics and phase‐change memory applications. The atomistic origin of their unusual property portfolio remains somewhat unclear, however, even though different and sometimes conflicting chemical‐bonding concepts have been introduced in the recent years. Here, it is proposed that projecting phononic force‐constant tensors for pairs of atoms along differing directions and ranges provide a suitable and quantitative descriptor of the bonding nature for these materials. In combination with orbital‐based quantitative measures of covalency such as crystal orbital Hamilton populations (COHP), it is concluded that the well‐established many‐center and even n‐center bonding is an appropriate picture of the underlying quantum‐chemical bonding mechanism, supporting the recent proposal of hyperbonded phase‐change materials.

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Long‐Range Forces in Rock‐Salt‐Type Tellurides and How they Mirror the Underlying Chemical Bonding

et al. 2021

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Bi₆₅Cu₁₃Ge₄₁O₆Br₁₂₂, a Low‐Valent Compound of High Structural Complexity Featuring the Trigonal Anion [O(Ge^IIBr₂)₃]^2–with an sp²‐Hybridized μ₃‐Oxide Ion

Gerisch

Isaeva

Ruck

2013

Zeitschrift anorg allge chemie

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Thiny black air-sensitive crystals of Bi 65 Cu 13 Ge 41 O 6 Br 122 = (Bi 5 ) 2 (Bi 9 ) 6 [O(GeBr 2 ) 3 ] 6 [Cu 6 Ge 5 Br 20 ][BiCu 7 Ge 18 Br 66 ] were obtained by very slow cooling of a melt of bismuth, bismuth tribromide, copper, and partly oxidized germanium. The crystal structure was described in the hexagonal space group P6 3 (no. 173) with a = 2584.2(4) pm and c = 1277.4(3) pm at 296(1) K. The polarity of the structure is subtle; large parts of the structure show a pseudo mirror plane. The highly diversified structure comprises five distinct structural fragments. For the first time, two polyhedral bismuth polycations, Bi 5 3+ (trigonal bipyramid, D 3h ) and Bi 9 5+ (tricapped trigonal prism, D 3h ), occur in one and the same chemical compound. A hitherto unknown group is the C 3h -symmetric μ 3 -oxido-tris[dibromidogermanate(II)] anion [O(GeBr 2 ) 3 ] 2-, in which the germanium atoms of three Ge II Br 2 units bind to a central oxide ion with sp 2 hybridization. Density-functionaltheory-based calculations on an isolated [O(GeBr 2 ) 3 ] 2anion confirm 2749 the stability of the group and its shape. Real-space chemical bonding analysis supports the polar nature of the Ge-O and Ge-Br bonds as well as the assigned oxidation states. The [O(GeBr 2 ) 3 ] 2anion and the bismuth polycations are embedded between two kinds of one-dimensional networks, which are running parallel to the c axis, a bromidocuprate(I)-germanate(II) network 1 ϱ [Cu 6 Ge 5 Br 20 ] 4and a bromido-bismuthate(III)-cuprate(I)-germanate(II) network 1 ϱ [BiCu 7 Ge 18 Br 66 ] 20-. The latter features pentacoordinate germanium(II) atoms with bond angles close to 90°. The solution of the crystal structure from X-ray diffraction data was hampered not only by severe pseudo-symmetry and the similar scattering power of copper, germanium, and bromine atoms, but also by substantial atomic disorder and orientational disorder of the Bi 5 3+ polycation. Bi 65 Cu 13 Ge 41 O 6 Br 122 may be seen as a link between low-valent germanium compounds and low-valent bismuth compounds.

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Fluorinated Ylides/Carbenes and Related Intermediates from Phosphonium/Sulfonium Salts

Lin

Xiao

2020

Acc. Chem. Res.

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Metrics & MoreArticle Recommendations CONSPECTUS: Owing to the special effects of the fluorine element, including high electronegativity and small atomic radius, the incorporation of a fluorinated group into organic molecules may modify their physical, chemical, and biological properties.Fluorine-containing compounds have found widespread application in a variety of areas, and thus, the development of efficient reagents and methods for the incorporation of fluorinated groups has become a subject of significant interest. Described in this Account are our recent discoveries in the chemistry of fluorinated ylides/carbenes and related intermediates generated from phosphonium/sulfonium salts. Initially, we obtained the (triphenylphosphonio) difluoroacetate, Ph 3 P + CF 2 CO 2 − (PDFA), which was proposed as a reactive intermediate but had never been successfully synthesized. PDFA, shelf-stable and easy to prepare, is not only a mild ylide (Ph 3 P + CF 2 − ) reagent, but also an efficient difluorocarbene source. It can directly generate difluorocarbene, via the first generation of ylide Ph 3 P + CF 2 − , simply under warming conditions without the need for any additive. Interestingly, difluorocarbene chemistry was then discovered by using PDFA as a reagent. Difluorocarbene can be oxidized to CF 2  O, can react with elemental sulfur to afford CF 2 S, and can be trapped by NaNH 2 or NH 3 to give CN − . The development of these processes into synthetic tools allowed us to achieve various reactions, including the challenging 18 F-trifluoromethylthiolation and cyanodifluoromethylation. It was found that a substituent on the cation of a phosphonium salt can be directly transferred as a nucleophile despite the cation's high electrophilicity. This transfer process is like an "umpolung" of the cation, which may provide more opportunities for the synthetic utilities of phosphonium salts. The investigation of this transfer process led us to find that iodophosphonium salts, active intermediates which can be easily generated, may efficiently promote deoxygenative functionalizations of aldehydes and alcohols. Dehydroxylative substitution of alcohols by this protocol permits the use of unprotected amines with higher pK a values as nucleophiles, which is an attractive feature compared with the Mitsunobu reaction. On the basis of the ylide-tocarbene process (Ph 3 P + CF 2 − → :CF 2 ), we further developed sulfonium salts as precursors of fluorinated ylides and fluorinated methyl carbenes. In particular, the studies on difluoromethylcarbene, remaining largely unexplored, may deserve more attention. The discoveries may find utility in the synthesis of biologically active fluorine-containing molecules.

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Hypervalent Molecules

Cited by 4 publications

References 79 publications

Long‐Range Forces in Rock‐Salt‐Type Tellurides and How they Mirror the Underlying Chemical Bonding

Long‐Range Forces in Rock‐Salt‐Type Tellurides and How they Mirror the Underlying Chemical Bonding

Bi₆₅Cu₁₃Ge₄₁O₆Br₁₂₂, a Low‐Valent Compound of High Structural Complexity Featuring the Trigonal Anion [O(Ge^IIBr₂)₃]^2–with an sp²‐Hybridized μ₃‐Oxide Ion

Fluorinated Ylides/Carbenes and Related Intermediates from Phosphonium/Sulfonium Salts

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Hypervalent Molecules

Cited by 4 publications

References 79 publications

Long‐Range Forces in Rock‐Salt‐Type Tellurides and How they Mirror the Underlying Chemical Bonding

Long‐Range Forces in Rock‐Salt‐Type Tellurides and How they Mirror the Underlying Chemical Bonding

Bi65Cu13Ge41O6Br122, a Low‐Valent Compound of High Structural Complexity Featuring the Trigonal Anion [O(GeIIBr2)3]2–with an sp2‐Hybridized μ3‐Oxide Ion

Fluorinated Ylides/Carbenes and Related Intermediates from Phosphonium/Sulfonium Salts

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Bi₆₅Cu₁₃Ge₄₁O₆Br₁₂₂, a Low‐Valent Compound of High Structural Complexity Featuring the Trigonal Anion [O(Ge^IIBr₂)₃]^2–with an sp²‐Hybridized μ₃‐Oxide Ion