A Unique Crystalline-State Reaction of an Overcrowded Distibene with Molecular Oxygen:  The First Example of a Single Crystal to a Single Crystal Reaction with an External Reagent

Tokitoh, Norihiro; Arai, Y.; Sasamori, Takahiro; Okazaki, Renji; Uekusa, Hidehiro; Ohashi, Yuji

doi:10.1021/ja973295y

Cited by 192 publications

(130 citation statements)

References 14 publications

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“…Another landmark in the research in this field was the preparation of the dibismuthene RBi=BiR as an analogue of alkenes with a double bond between bismuth atoms by Okazaki and Tokitoh, [6] which was shortly followed by the isolation of antimony analogue RSb=SbR. [7] Power et al reported functionality in the pendant arm of one of the ligands was observed. The reduction of compound 2 with an excess amount of magnesium was strongly dependent on the reaction time.…”

Section: Introductionmentioning

confidence: 99%

On the Reduction of NC Chelated Organoantimony(III) Chlorides

et al. 2011

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The conversion of organolithium compound LLi, for which L = [o‐C6H4(CH=NC6H3iPr2‐2,6)]–, with antimony chloride gave the molecular chlorides LSbCl2 (1) and L2SbCl (2) depending on the molar ratio used (either 1:1 or 2:1). Bothcompounds were characterized by using 1H and 13C NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. The reaction of 1 with two molar equivalents of K[B(sBu)3H] led to smooth formation of compound L4Sb4 (3) as a result of hydrogen elimination from the unstable hydrido compound. On the contrary, a similar reaction between 2 and K[B(sBu)3H] (1:1) did not result in hydrogen elimination and the formation of expected distibine L2SbSbL2, but an addition of an in situ generated L2Sb–H bond across the C=N functionality in the pendant arm of one of the ligands was observed. The reduction of compound 2 with an excess amount of magnesium was strongly dependent on the reaction time. The distibine L2SbSbL2 (5) could be isolated after 4–5 h from this reaction mixture. Elongation of the reaction time to 1 d (and more) gave a more complicated reaction mixture, in which three products, distibine 5, compound 3 and organomagnesium compound L2Mg(THF) (6), were characterized by single‐crystal X‐ray diffraction in addition to other unidentified products. These results can be rationalized by a migration of the ligand L from the antimony atom to the magnesium, thus explaining formation of both L4Sb4 (3) compound and L2Mg(THF) (6).

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Section: Introductionmentioning

confidence: 99%

On the Reduction of NC Chelated Organoantimony(III) Chlorides

et al. 2011

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“…• C in a sealed tube for 48 h. The triethylamine seems to play an important role in the sulfurization reaction, and the role of which can be explained by activation of elemental sulfur in benzene-d 6 . The 31 P NMR spectrum of 2b in benzene-d 6 displayed a singlet signal at −72.9 ppm, which is quite similar to those of thiadiphosphiranes 2c [8] and 2d [18] (Table 1).…”

Section: Reactions Of Diphosphenes 1a and 1b With Elemental Sulfurmentioning

confidence: 99%

“…Thiadiphosphirane 2b was very robust in the open air, and no decomposition was observed. On the other hand, the reaction of 1a with elemental sulfur in benzene-d 6 at room temperature for 30 min resulted in the formation of the corresponding thiadiphosphirane 2a as yellow crystals in 84% isolated yield (Scheme 1), showing higher reactivity of 1a toward elemental sulfur than that of 1b. Although 2a was stable under an argon atmosphere, gradual decomposition of 2a was observed in the open air in contrast to the case of 2b.…”

Section: Reactions Of Diphosphenes 1a and 1b With Elemental Sulfurmentioning

confidence: 99%

“…We have also succeeded in the synthesis of novel doubly bonded systems between heavier group 15 elements, that is, diphosphene ( P P ), distibene ( Sb Sb ), dibismuthene ( Bi Bi ), phosphabismuthene ( P Bi ), and stibabismuthene ( Sb Bi ), by taking advantage of efficient steric protection groups, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris-(trimethylsilyl)methyl]phenyl (Bbt) groups ( Fig. 1) [5][6][7][8][9][10][11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

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Chalcogenation reactions of a stable ferrocenyldiphosphene: Formation of thia‐, selena‐, and telluradiphosphiranes

Nagahora

Sasamori

Tokitoh

2008

Heteroatom Chemistry

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“…In the gas phase, tetramers were also detected by mass spectrometry. 3 We report here on the trapping of the dimer, cyclo-R 4 ] (nbd = norbornadiene).…”

Section: Introductionmentioning

confidence: 99%

Communication: A complex with the cyclo‐R₂Sb₂S₂ [R = CH(SiMe₃)₂] ligand

Breunig

Ghesner

Lork

2002

Applied Organom Chemis

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The reaction of the cyclo oligomers R nSb nS n [n = 2, 3; R = CH(SiMe3)2] with W(CO)5thf (thf = tetrahydrofuran) in thf results in trapping of the dimer in cyclo‐[R2Sb2S2][W(CO)5]2 (1). An X‐ray crystal structure analysis revealed that the complex contains a four‐membered antimony–sulfur ring in an almost planar conformation, where the alkyl groups occupy cis positions and the W(CO)5 units are bonded trans to the alkyl groups on the antimony atoms. Copyright © 2002 John Wiley & Sons, Ltd.

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A Unique Crystalline-State Reaction of an Overcrowded Distibene with Molecular Oxygen: The First Example of a Single Crystal to a Single Crystal Reaction with an External Reagent

Cited by 192 publications

References 14 publications

On the Reduction of NC Chelated Organoantimony(III) Chlorides

On the Reduction of NC Chelated Organoantimony(III) Chlorides

Chalcogenation reactions of a stable ferrocenyldiphosphene: Formation of thia‐, selena‐, and telluradiphosphiranes

Communication: A complex with the cyclo‐R₂Sb₂S₂ [R = CH(SiMe₃)₂] ligand

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A Unique Crystalline-State Reaction of an Overcrowded Distibene with Molecular Oxygen: The First Example of a Single Crystal to a Single Crystal Reaction with an External Reagent

Cited by 192 publications

References 14 publications

On the Reduction of NC Chelated Organoantimony(III) Chlorides

On the Reduction of NC Chelated Organoantimony(III) Chlorides

Chalcogenation reactions of a stable ferrocenyldiphosphene: Formation of thia‐, selena‐, and telluradiphosphiranes

Communication: A complex with the cyclo‐R2Sb2S2 [R = CH(SiMe3)2] ligand

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Communication: A complex with the cyclo‐R₂Sb₂S₂ [R = CH(SiMe₃)₂] ligand