Synthesis of 1‐Phospha‐2‐boraacenaphthenes: Reductive 1,2‐Aryl Migration of 1‐Diarylboryl‐8‐dichlorophosphinonaphthalenes

Tsurusaki, Akihiro; Sasamori, Takahiro; Wakamiya, Atsushi; Yamaguchi, Shigehiro; Nagura, Kazuhiko; Irle, Stephan; Tokitoh, Norihiro

doi:10.1002/ange.201104971

Cited by 19 publications

(22 citation statements)

References 49 publications

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“…They are the starting and end points of a combined experimental and theoretical simulation of the reaction along a pseudoreaction coordinate. We note in passing that cation 2 isolated herein is isoelectronic to very recently reported neutral peri ‐substituted (ace)naphthylphosphinoboranes [1‐R 2 P‐Nap‐8‐BR′ 2 ] and [5‐R 2 P‐Ace‐6‐BR′ 2 ] (R= i Pr, Ph, mesityl, Cl), which adopt two different structure types, namely, regular Lewis pairs with short bonding P−B interactions and frustrated Lewis pairs with long nonbonding P−B contacts, as well as the 1,8‐diphenylphosphoniumnaphthalene dication [1,8‐Ph 2 P‐Nap] 2+ (Scheme ) …”

Section: Resultssupporting

confidence: 61%

Mapping the Trajectory of Nucleophilic Substitution at Silicon Using aperi‐Substituted Acenaphthyl Scaffold

Hupf

Olaru

Raţ

et al. 2017

Chemistry A European J

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The second-order nucleophilic substitution (S 2) reaction at a silicon atom is scrutinized by means of snapshots along a pseudoreaction coordinate. Phosphine and fluoride represent both attacking and leaving groups in the modeled S 2 reaction. In the experimentally obtained 5-diphenylphosphinoacenaphth-6-yl-dimethylfluorosilane, 1, the phosphine and fluorosilane moieties are forced into immediate proximity through an acenaphthyl scaffold, that is, they exhibit peri interactions that serve as the model of the reactant ion-molecule complex and starting point for a theoretical potential-energy surface (PES) scan. Upon dissociation of fluoride, the experimentally obtained silylphosphonium cation 2 serves as a model of the product and end point of the PES scan. The pseudoreaction pathway is studied using geometric, energetic, spectroscopic, molecular-orbital, and topological real-space bonding indicators. It becomes evident that it is crucial to combine such methods to understand the pseudoreaction because they reveal different aspects based on different sensitivity to dispersive, electrostatic, and polar-covalent contributions to bonding, as shown by the reduced density gradient analysis. For example, atoms-in-molecules theory describes a late topological catastrophe, whereas the electron localizability indicator describes an early concerted reaction and natural resonance theory describes a more gradual change of properties. This case study encourages the use of a well-balanced toolbox equipped with complementary methods to emphasize different aspects of bonding.

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Section: Resultssupporting

confidence: 61%

Mapping the Trajectory of Nucleophilic Substitution at Silicon Using aperi‐Substituted Acenaphthyl Scaffold

Hupf

Olaru

Raţ

et al. 2017

Chemistry A European J

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“…Inspection of the E−P peri distances of 1−9 reveals some unexpected trends. The B−P distance of 1 (2.040(2) Å) compares well with those of the related phosphinoboranes Ia (2.108(2) Å), 3,4 IIa (2.173(3) Å), IIb (2.011(2) Å), 5 and IIIa (2.162(2) Å). 6,7 However, the Al−P distance of 2 (2.4305(5) Å) is exceptionally longer than expected; it is slightly longer than the Ga−P distance of 3 (2.411(2) Å) and even substantially longer than the P−P distance of 6 (2.252(1) Å).…”

Section: Organometallicsmentioning

confidence: 78%

“…No reaction of ArSnBu 3 with AlCl 3 and PCl 3 occurred. The reaction of 3 gave several products that were difficult to separate. One of the products in the reaction with BiCl 3 could be assigned to ArBu 2 SnCl on the basis of the 31 P NMR signal at δ −31.1 ppm that showed indicative tin satellites (J( 31 P-119/117 Sn) = 595/569 Hz).…”

Section: ■ Introductionmentioning

confidence: 98%

Probing Donor–Acceptor Interactions inperi-Substituted Diphenylphosphinoacenaphthyl–Element Dichlorides of Group 13 and 15 Elements

et al. 2014

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Transmetalation reactions of ArLi with ECl 3 (E = Al, P, In, Bi) and ArSnBu 3 with ECl 3 (E = B, Ga, Tl, As, Sb) gave rise to the formation of peri-substituted diphenylphosphinoacenaphthyl−element dichlorides ArECl 2 (Ar = 6-Ph 2 PAce-5-), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations were performed on the compounds at relaxed gas-phase molecular geometries. For the series ArECl 2 containing group 13 elements one structure type featuring regular Lewis pairs with short E−P peri distances (E = B, Al, Ga, In, Tl) was observed. For the series ArECl 2 containing group 15 elements two structural types with very different peri distances (E = P, As, Sb, Bi) were found. The computed electron and pair densities were topologically analyzed according to the atoms-in-molecules (AIM) and electron localizability indicator (ELI-D) spacepartitioning schemes, which facilitates the characterization of the peri interactions and also allows for monitoring minute electronic effects induced by different substituents and/or spatial arrangements. ■ INTRODUCTIONDonor−acceptor interactions between phosphines and maingroup elements have received tremendous interest, 1 which has been recently fueled by the discovery that bulky phosphines and boranes may form frustrated Lewis pairs (FLPs) that are able to activate small molecules, such as dihydrogen and carbon dioxide, without the aid of a transition metal. 2 Peri-substituted (ace)naphthylphosphinoboranes comprise regular Lewis pairs or FLPs depending on the nature of the substituents attached to the B and P atoms in 1,8-and 5,6-positions (Chart 1). Sasamori and Tokitoh et al. 3 communicated two 1-dichlorophosphino-8-naphthyl-diarylboranes 1-(Cl 2 P)-8-(R 2 B)-Nap (Ia, R = 3,5-t-Bu 2 C 6 H 3 ; Ib, R = Mes) and later disclosed structural data. 4 Reduction of Ia,b with Mg proceeded with aryl group migration and gave rise to the formation of unique phosphaboranes. 3 Miqueu and Bourissou et al. 5 reported on the three 1-diisopropylphosphino-8-naphthyl-diorganoboranes 1-(iPr 2 P)-8-(R 2 B)-Nap (IIa, R = Mes; IIb, R = Cy; IIc, R 2 = Flu; Flu = 2,2′-biphenylene), which were structurally elucidated. The different P−B peri distances (Å) of 2.108(2) (Ia), 2.892(2) (Ib), 2.173(3) (IIa), 2.076(2) (IIb), and 2.011(2) (IIc) demonstrate that the bulk and electronic effect of the substituents attached to the B and P atoms determines the nature of the peri interaction: namely, if it is dominated by attractive or repulsive forces.Our group described 1-diphenylphosphino-8-naphthyl-dimesitylborane (1-(Ph 2 P)-8-(Mes 2 B)-Nap, IIIa) and the closely related 5-diphenylphosphino-6-acenaphthyl-dimesitylborane (5-(Ph 2 P)-6-(Mes 2 B)-Ace, IIIb), possessing the same substituents at the B and P atoms with albeit quite different B−P peri distances of 2.162(2) and 3.050(3) Å, which is due to the fact that the naphthyl framework accommodates a higher degree of conformational flexibility in comparison to the rigid acenaphthyl framework. 6 Wang et al. also conducted an ...

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“…Diarylboryl-8-dichlorophosphinonaphthalenes 2 a,b were prepared from 1,8-dibromonaphthalene in two steps. [8] The X-ray crystallographic analyses of 2 a,b (Figure 1 a and b) showed the longer PÀB distance of 2 a (2.892(2), 2.961(2) ) than that of 2 b (2.108(2) ), suggesting negligible intramolecular PÀB coordination in 2 a due to the steric congestion in contrast to the concrete PÀB coordinate bond in 2 b. Thus, it should be noted that the boron atom of 2 a surrounded by mesityl (Mes) groups should be more congested than that of 2 b bearing two 3,5-di-tert-butylphenyl (Dtp) groups.…”

Section: Resultsmentioning

confidence: 99%

“…[3,5] A series of kinetically stabilized phosphinoboranes bearing mesityl, phenyl, trimethylsilyl, and 1-adamantyl groups have been reported by Power et al, [6] whereas phosphinoboranes thermodynamically stabilized by coordination of a Lewis acid and base, [(LA)H 2 PÀBH 2 (LB)]) (LA = Lewis acid, LB = Lewis base), have been reported by Scheer et al [7] We report here the synthesis and properties of 1-phospha-2-boraacenaphthene 1, which is a unique heterocyclic compound bearing a PÀB bond tethered with a naphthyl unit at the 1,8-posi-tions. [8] On the basis of the previous reports on the chalcogenation reactions of phosphinoborane derivatives shown in Scheme 1,[7c,9] the chalcogenation reaction of 1 would be expected to afford unique heterocyclic compounds containing a P(Ch)ÀChÀB (Ch=S, Se) moiety. Thus, we have examined the sulfurization and selenization reactions of 1 in the expectation of synthesis of new heterocyclic compounds containing P, B, and chalcogen atoms.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of a 1‐Phospha‐2‐boraacenaphthene Derivative and Its Chalcogenation Reactions

Tsurusaki¹,

Sasamori²,

Tokitoh³

2014

Chemistry A European J

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The first stable 1-phospha-2-boraacenaphthene 1 was synthesized by the reduction of 1-dimesitylboryl-8-dichlorophosphinonaphthalene (2a) with elemental magnesium, and it was fully characterized. The chalcogenation reaction of 1 with elemental sulfur or selenium afforded the unique heterocycles, 2-thia- and 2-selena-1-phospha-3-boraphenalenes 9S and 9Se, respectively, through the insertion of the chalcogen atom into a P-B bond of 1. Further chalcogenation of 9 afforded the corresponding phosphine chalcogenides. These newly obtained chalcogenated compounds have been characterized. The unique dynamic behavior of 2-chalcogena-1-phospha-3-boraphenalene-1-chalcogenides 10 in solution has also been described.

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Synthesis of 1‐Phospha‐2‐boraacenaphthenes: Reductive 1,2‐Aryl Migration of 1‐Diarylboryl‐8‐dichlorophosphinonaphthalenes

Cited by 19 publications

References 49 publications

Mapping the Trajectory of Nucleophilic Substitution at Silicon Using aperi‐Substituted Acenaphthyl Scaffold

Mapping the Trajectory of Nucleophilic Substitution at Silicon Using aperi‐Substituted Acenaphthyl Scaffold

Probing Donor–Acceptor Interactions inperi-Substituted Diphenylphosphinoacenaphthyl–Element Dichlorides of Group 13 and 15 Elements

Synthesis and Structure of a 1‐Phospha‐2‐boraacenaphthene Derivative and Its Chalcogenation Reactions

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