Structure and Characterization of 9,10-Diethyl-9,10-diphospha-9,10-dihydroanthracene as an Electron Donor

Akutsu, Hiroki; Ogasawara, Masamichi; Saburi, Masahiko; Kozawa, Kozo; Uchida, T.

doi:10.1246/bcsj.69.1223

Cited by 13 publications

(12 citation statements)

References 7 publications

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“…They showed that the dibenzo[b,b]1,4‐dihydro‐1,4‐diphosphinines IIa , b (a: R = Ph; b: R = Et) could be obtained by stepwise, base‐initiated ring closure using dichloro(organo)phosphanes. Later on, Uchida added a further simplification to the synthetic protocol of IIb . The synthesis of I was achieved by Märkl by the reaction of diethynylphosphane with a primary phosphane, which led to new P‐substituted derivatives.…”

Section: Introductionmentioning

confidence: 99%

“…Similarly, compound IV was obtained by the thermal reaction of the corresponding backbone, dichlorophosphanyl‐substituted 1‐methyl‐2‐alkyl‐imidazole, with pyridine (as the base), thus leading to the tricyclic heterocyclic scaffold shown in Figure . Hitherto, surprisingly few reactivity studies have been reported on mono‐, bi‐, or tricyclic 1,4‐dihydro‐1,4‐diphosphinines relying exclusively on derivatives possessing exocyclic P–C single bonds,, thus significantly restricting the opportunities of P functionalization.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Substitution, and Oxidation of Imidazole‐2‐thione Based Tricyclic 1,4‐Dihydro‐1,4‐diphosphinines

et al. 2018

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Herein, the synthesis and chemistry of P-functional tricyclic 1,4-dihydro-1,4-diphosphinines is described, following a recent communication on their use as precursors of 1,4-diphosphinines. In particular, ring formation of imidazole-2thione-based tricyclic 1,4-dihydro-1,4-diphosphinines 4a,b {-[P(Me 2 N)IMS R,R ] 2 -; IMS R,R = 1,3-dialkylimidazole-2-thione-4-yl}, first detected as side products, has been optimized to access 4d-f {-[P(Et 2 N)IMS R,R ] 2 -; IMS R,R = 1,3-dialkylimidazole-2-thione-4-yl}. The 1,4-dihydro-1,4-dichloro-1,4-diphosphinines 8a,b {-[P(Cl)IMS R,R ] 2 -; IMS R,R = 1,3-dialkylimidazole-2-thione-4-yl}, easily obtained from 4, are ideal starting materials for P-substituted products 9a-c (P-R; R = nBu, TMSC 2 -). The P-diorgano- [a] azole-2-derivatives, we recently described the first examples of tricyclic imidazole-2-thiones V having P-diethylamino groups ( Figure 1). [15] In the same short report, we also demonstrated a reductive conversion of P-Cl functional 1,4-dihydro-1,4-diphosphinines to give first examples of isolable 1,4-diphosphinines. [15] Following this short communication, we here report on detailed investigations on optimized synthetic protocols, as well as broad reactivity studies of P-functional tricyclic 1,4-dihydro-1,4-diphosphinines, to pave the way for their future use as unique ligands in coordination chemistry. Some reaction pathways and bonding situations have also been examined using DFT calculations. Results and DiscussionRecently, we demonstrated that backbone phosphanylation of imidazole-2-thiones allows access to acyclic dialkylaminobis(imidazole-2-thione-4-yl)phosphanes. [14] But in this study only imidazole-2-thiones with secondary or tertiary alkyl groups on either N-atoms (or at least on one) were used, and the final products were obtained in excellent yields without any byproducts. Interestingly, when 1,3-dimethyl imidazole-2-thione 1a, n-butyllithium, and dichloro(dimethylamino)phosphane 2a are used in THF, a white precipitate forms alongside the main product 3a (Scheme 1). The 31 P NMR spectrum shows the signal for the acyclic compound 3a (δ =14.4 ppm) and two resonance signals at δ = 9.8 and 10.2 ppm that are assigned to the cis and trans stereoisomers of 1,4-dihydro-1,4-diphosphinines 4a,a′ (ratio 1:1.3), according to the relative positioning of the P-NMe 2 groups. The trans isomer of 4a is easily isolated from the isomeric mixture by washing the precipitate with THF, because of the higher solubility of the cis isomer, and hence, it can be unambiguously characterized, possessing a 31 P resonance at NMR spectrum at 9.4 ppm (CDCl 3 ); the value is slightly upfieldshifted, compared with the reported derivatives IV (15.1-15.6 ppm [9] ).When the reaction is performed using 1,3-diethyl-imidazole-2-thione 1b, n-butyllithium and dichloro(dimethylamino)phosphane under the same conditions, a mixture of 3b and 4b is obtained (ratio 3:1), which is separable by column chromatography. The 31 P{ 1 H} NMR spectra of 3b and 4b (in CDCl 3 ) show similar chemical shifts as f...

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, Substitution, and Oxidation of Imidazole‐2‐thione Based Tricyclic 1,4‐Dihydro‐1,4‐diphosphinines

et al. 2018

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“…The 1,4‐dihydro‐1,4‐diphosphinines, though well‐known since 1964, reactivity studies have received little attention. Recently, we reported on a new class of imidazole‐2‐thione‐based tricyclic 1,4‐dihydro‐1,4‐diphosphinines and their conversion into 1,4‐diphosphinines using dedichlorination under mild conditions .…”

Section: Introductionmentioning

confidence: 99%

The Quest for Twofold Reductive P–C Bond Cleavage of P–Ph Substituted 1,4‐Dihydro‐1,4‐diphosphinine Derivatives

et al. 2018

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It is demonstrated that backbone chloro(phenyl)phosphanyl-substituted imidazole-2-thiones 3 (N-R = Me, Et, nBu) can be easily synthesized which allow for a selective access to tricyclic 1,4-diphenyl-1,4-dihydro-1,4-diphosphinines 5 via reaction with LDA. Furthermore, new examples for preferred substitution reactions are provided that occurred when KHMDS was used thus yielding P-N(SiMe 3 ) 2 substituted derivatives 4.[a]

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“…1 H (400 MHz) and 13 C (100 MHz) NMR spectra were recorded on a JEOL EX400 spectrometer, and samples were analyzed in CDCl 3 using tetramethylsilane as an internal standard. Elemental analyses were performed at the Microanalytical Center of Kyoto University.…”

Section: Experimental Generalmentioning

confidence: 99%

“…The 1,4-dihydro-1,4-diarsinines are stable toward air and moisture. Cyclic organophosphorus [12] or organonitrogen [13][14][15][16] compounds, which are similar analogues of 1,4-dihydro-1,4-diarsinines, are too redox-active as ligands because of their two ethylene bridges. On the other hand, cyclic organoarsenic compounds similar to cis-1,4-dihydro-1,4-diarsinines such as 5,l0-dihydroarsanthren were synthesized [17].…”

Section: Introductionmentioning

confidence: 99%

Structural diversity in the coordination of 1,4‐dihydro‐1,4‐diarsinine as a cyclic ditopic organoarsenic ligand to metal ions

Arita¹,

Naka²,

Morisaki³

et al. 2011

Heteroatom Chemistry

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A number of different complexation structures of cis‐1,4‐dihydro‐1,4‐dimethyl‐2,3,5,6‐tetrakis(t‐butoxycarbonyl)‐1,4‐diarsinine (cis‐DHDAtBu) with gold(I) and iridium(III) were synthesized and characterized by 1H, 13C NMR spectra, X‐ray crystallography, and elemental analysis. Mono‐ and di‐nuclear gold(I) chloride complexes with cis‐DHDAtBu were obtained by simple addition of gold(I) chloride to cis‐DHDAtBu. A hetero‐trinuclear gold‐platinum‐gold complex (PtAu2Cl4(cis‐DHDAtBu)2) was obtained by complexation of a mononuclear platinum(II) complex (trans‐PtCl2(cis‐DHDAtBu)2), which was obtained by complexation of cis‐DHDAtBu with a half‐equimolar amount of PtCl2(PhCN)2, with a twice‐equimolar amount of gold(I) chloride. An iridium(III) complex with cis‐DHDAtBu (IrCl3(cis‐DHDAtBu)2) was prepared from hydrated iridium(III) chloride and cis‐DHDAtBu. The complex comprises a five‐membered chelate cis‐DHDAtBu and an usual monodentate cis‐DHDAtBu. The interior angles at around the arsenic and the As–C—C bond angles were significantly varied from 113.4° to 129.4° in the present crystal. These observations suggest that the flexibility of the bond angles at around the arsenic center is inherent property in the present organoarsenic compounds. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 23:16–26, 2012; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20747

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Structure and Characterization of 9,10-Diethyl-9,10-diphospha-9,10-dihydroanthracene as an Electron Donor

Cited by 13 publications

References 7 publications

Synthesis, Substitution, and Oxidation of Imidazole‐2‐thione Based Tricyclic 1,4‐Dihydro‐1,4‐diphosphinines

Synthesis, Substitution, and Oxidation of Imidazole‐2‐thione Based Tricyclic 1,4‐Dihydro‐1,4‐diphosphinines

The Quest for Twofold Reductive P–C Bond Cleavage of P–Ph Substituted 1,4‐Dihydro‐1,4‐diphosphinine Derivatives

Structural diversity in the coordination of 1,4‐dihydro‐1,4‐diarsinine as a cyclic ditopic organoarsenic ligand to metal ions

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