Synthesis and structural characterization of a photoresponsive organodirhodium complex with active S–S bonds: [(CpPhRh)2(μ-CH2)2(μ-O2SSO2)] (CpPh=η5-C5Me4Ph)

Miyano, Yousuke; Nakai, Hidetaka; Hayashi, Yoshihito; Isobe, Kiyoshi

doi:10.1016/j.jorganchem.2006.08.063

Cited by 15 publications

(5 citation statements)

References 10 publications

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“…In the case of sec -butyl, more peaks are seen due to the presence of a chiral center on the ligand. All complexes synthesized exhibited a typical piano-stool arrangement with chloro bridges between the metal centers and a terminal chloride bound to the metal, similarly to other reported iridium and rhodium dimers. ,,,− …”

Section: Resultssupporting

confidence: 76%

Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes

2016

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The present work describes the design and synthesis of a series of rhodium and iridium dimers [(η 5ring)MCl] 2 (μ 2 -Cl) 2 (where (η 5 -ring)MCl = (η 5 -Me 4 C 5 R)Rh-(III)Cl or (η 5 -Me 4 C 5 R)Ir(III)Cl) using a new and efficient 1 h procedure. Rhodium and iridium dimeric complexes were synthesized via a microwave reaction. The modified HMe 4 C 5 R (R = isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, n-hexyl, nheptyl, n-octyl, phenyl, benzyl, phenethyl, cyclohexyl, and cyclopentyl) type ligands were synthesized by reaction of 2,3,4,5-tetramethylcyclopent-2-en-1-one with the respective Grignard reagent (RMgX), followed by elimination of water under acidic conditions to produce the tetramethyl(alkyl or aryl)cyclopentadienes in moderate to excellent yields (40−98%). Reaction of the HMe 4 C 5 R ligands with [M(COD)](μ 2 -Cl) 2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) gave the dimeric complexes [(η 5 -Me 4 C 5 R)MCl] 2 (μ 2 -Cl) 2 in yields ranging from 47% to 96%. The derivatized dimers were tested for antimicrobial activity, showing activity against Mycobacterium smegmatis and improved activity with derivatized R groups against Staphylococcus aureus and MRSA 43300. The characterization of these complexes was completed by NMR spectroscopy, single-crystal X-ray diffraction, high-resolution mass spectrometry, and elemental analysis.

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Section: Resultssupporting

confidence: 76%

Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes

2016

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“…Similarly, dithionite ligands (O 2 SSO 2 ) are predicted to isomerize to give isodithionite ligands (O 2 SOSO). This last process well describes what occurs in the experimentally observed , photoconversion of Cp* 2 Rh 2 (μ-CH 2 ) 2 (μ-O 2 SSO 2 ) to the isodithionite complex Cp* 2 Rh(μ-CH 2 ) 2 (μ-O 2 SOSO). Finally ethylene, methylcarbene, and SO 2 can function as either terminal or bridging ligands.…”

Section: Discussionsupporting

confidence: 80%

“…However, it functions as a chelating ligand through its sulfur atoms in the cyclopentadienylrhodium complexes Cp 2 Rh 2 (μ-CH 2 ) 2 (μ-S 2 O 4 ) [Cp = η 5 -Me 5 C 5 (=Cp*) or η 5 -EtMe 4 C 5 (=Cp Et ); Figure ]. − These species exhibit an unusual type of photochromism involving rearrangement of the coordinated dithionite ligand [O 2 SSO 2 ] 2– into an isomeric [O 2 SOSO] 2– “isodithionite” ligand in which a terminal oxygen atom is inserted into the S–S bond of the original dithionite ligand. Such an “isodithionite” ligand is unknown in the uncomplexed form.…”

Section: Introductionmentioning

confidence: 99%

Binuclear Cyclopentadienylmetal Methylene Sulfur Dioxide Complexes of Rhodium and Iridium Related to a Photochromic Metal Dithionite Complex

et al. 2017

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The photochromic dithionite complex Cp*Rh(μ-CH)(μ-OSSO) (Cp* = η-MeC) is of interest because it undergoes an unusual fully reversible unimolecular photochemical rearrangement to the isodithionite complex Cp*Rh(μ-CH)(μ-OSOSO). In order to obtain more insight into these systems, a comprehensive density functional theory study has been carried out on isomeric CpM(CH)(SO) (M = Rh, Ir) derivatives. The experimentally observed rhodium complexes with coupled sulfur dioxide (SO) units to give dithionite or isodithionite ligands are surprisingly high-energy kinetic isomers in our analysis, reflecting the need for dithionite rather than SO for their synthesis. Many isomeric structures containing two separate SO ligands are found to lie at lower energies than these dithionite and isodithionite complexes. In the lowest-energy CpM(CH)(SO) isomers, the two methylene groups couple to form an ethylene ligand that can be either terminal or bridging. In slightly higher energy structures, a formal hydrogen shift is predicted to occur within the ethylene ligand to give a methylcarbene CHCH ligand. Isomers with a bridging methylcarbene ligand are energetically preferred over isomers with a terminal methylcarbene ligand. Generation of the lower-energy CpRh(CH)(SO) isomers containing separate SO ligands should be achievable through reactions of SO with more highly reduced cyclopentadienylrhodium methylene complexes such as Cp*Rh(μ-CH).

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“…Thus, in addition to the electron‐deficient nature, the presence of the pendant amide moiety may also facilitate the formal Lossen rearrangement. The use of Cp* Ph2 Rh III and Cp* Ph Rh III complexes further decreased the yields of 6 cb (entries 17 and 18), and the use of Cp* ligand afforded 8 cb exclusively (entry 19). Notably, no formal Lossen rearrangement/[3+2] annulation product 7 cb was generated in any of the cases studied.…”

Section: Resultsmentioning

confidence: 99%

Formal Lossen Rearrangement/Alkenylation or Annulation Cascade of Heterole Carboxamides with Alkynes Catalyzed by CpRh^III Complexes with Pendant Amides

Yamada

Shibata

Tanaka

2019

Chemistry A European J

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It has been established that a cyclopentadienyl (Cp) RhIII complex with two aryl groups and a pendant amide moiety catalyzes the formal Lossen rearrangement/alkenylation cascade of N‐pivaloyl heterole carboxamides with internal alkynes, leading to alkenylheteroles. Interestingly, the use of sterically demanding internal alkynes afforded not the alkenylation but the [3+2] annulation products ([5,5]‐fused heteroles). In these reactions, the pendant amide moiety of the CpRhIII complex may accelerate the formal Lossen rearrangement. The use of five‐membered heteroles may deter reductive elimination to form strained [5,5]‐fused heteroles; instead, protonation proceeds to give the alkenylation products. Bulky alkyne substituents accelerate the reductive elimination to allow the formation of the [5,5]‐fused heteroles.

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Synthesis and structural characterization of a photoresponsive organodirhodium complex with active S–S bonds: [(CpPhRh)2(μ-CH2)2(μ-O2SSO2)] (CpPh=η5-C5Me4Ph)

Cited by 15 publications

References 10 publications

Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes

Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes

Binuclear Cyclopentadienylmetal Methylene Sulfur Dioxide Complexes of Rhodium and Iridium Related to a Photochromic Metal Dithionite Complex

Formal Lossen Rearrangement/Alkenylation or Annulation Cascade of Heterole Carboxamides with Alkynes Catalyzed by CpRh^III Complexes with Pendant Amides

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Synthesis and structural characterization of a photoresponsive organodirhodium complex with active S–S bonds: [(CpPhRh)2(μ-CH2)2(μ-O2SSO2)] (CpPh=η5-C5Me4Ph)

Cited by 15 publications

References 10 publications

Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes

Rapid Access to Derivatized, Dimeric, Ring-Substituted Dichloro(cyclopentadienyl)rhodium(III) and Iridium(III) Complexes

Binuclear Cyclopentadienylmetal Methylene Sulfur Dioxide Complexes of Rhodium and Iridium Related to a Photochromic Metal Dithionite Complex

Formal Lossen Rearrangement/Alkenylation or Annulation Cascade of Heterole Carboxamides with Alkynes Catalyzed by CpRhIII Complexes with Pendant Amides

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Formal Lossen Rearrangement/Alkenylation or Annulation Cascade of Heterole Carboxamides with Alkynes Catalyzed by CpRh^III Complexes with Pendant Amides