Electrophilic Aromatic Substitution Reactions of a Metallabenzene: Nitration and Halogenation of the Osmabenzene [Os{C(SMe)CHCHCHCH}I(CO)(PPh3)2]

Rickard, Clifton E. F.; Roper, Warren R.; Woodgate, Scott D.; Wright, L. James

doi:10.1002/(sici)1521-3773(20000218)39:4<750::aid-anie750>3.0.co;2-q

Cited by 128 publications

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“…In the 1 H NMR spectrum in CD 2 Cl 2 , the OsC H signal was observed at δ =23.1 ppm and that of the γ‐C H signal at δ =8.6 ppm. The 1 H NMR chemical shift of the OsCH signal ( δ =23.1 ppm) is significantly downfield compared to those of Roper's osmabenzenes (usually less than 14 ppm),1, 5, 14 and the vinyl complex [Os(CHCHPh)Cl(CO)(PPh 3 ) 3 ] ( δ =8.32 ppm),15 but is close to those of osmium carbene complexes such as [OsC1 2 (CHCH 2 Ph)(CO)(P i Pr 3 ) 2 ] ( δ =18.99 ppm),16a [OsC1 2 {CHCHC(CH 3 ) 2 }(CO)(P i Pr 3 ) 2 ] ( δ =18.20 ppm),16a and [OsHCl(CHR)(CO)(P i Pr 3 ) 2 ] (R=H, δ =17.9, 16.9 ppm; R=Ph, δ =17.45 ppm; R=CO 2 Et, δ =17.22 ppm; R=SiMe 3 , δ =19.85 ppm) 16b. In the 13 C{ 1 H} NMR spectrum (in CD 2 Cl 2 ), the signals of Os C H, C PPh 3 , and γ‐ C H are observed at δ =239.7, 112.7, and 160.5 ppm, respectively.…”

Section: Resultsmentioning

confidence: 91%

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Synthesis, Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh₃ Substituents

Zhang

Lin

et al. 2009

Chemistry A European J

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Treatment of [OsCl(2)(PPh(3))(3)] with HC[triple bond]CCH(OH)C[triple bond]CH/PPh(3) produces the osmabenzene [Os{CHC(PPh(3))CHC(PPh(3))CH}Cl(2)(PPh(3))(2)][OH] (2), which is air stable in both solution and solid state. The key intermediate of the one-pot reaction, [OsCl(2){CH=C(PPh(3))CH(OH)C[triple bond]CH}(PPh(3))(2)] (3), and the related complex [Os(NCS)(2){CHC(PPh(3))CH(OH)C[triple bond]CH}(PPh(3))(2)] (7) have been isolated and characterized, further supporting the proposed mechanisms for the reaction. Reactions of 3 with PPh(3), NaI, and NaSCN give osmabenzene 2, iodo-substituted osmabenzene [Os{CHC(PPh(3))CHCICH}I(2)(PPh(3))(2)] (4), and thiocyanato-substituted osmabenzene [Os{CHC(PPh(3))CHC(SCN)CH}(NCS)(2)(PPh(3))(2)] (5) respectively. Similarly, reaction of [OsBr(2)(PPh(3))(3)] with HC[triple bond]CCH(OH)C[triple bond] CH in THF produces [OsBr(2){CH=C(PPh(3))CH(OH)C[triple bond]CH}(PPh(3))(2)] (9), which reacts with PPh(3)/Bu(4)NBr to give osmabenzene [Os{CHC(PPh(3))CHC(PPh(3))CH}Br(2)(PPh(3))(2)]Br (10). Ligand substitution reactions of 2 produce a series of new stable osmabenzenes 11-17. An electrochemical study shows that osmabenzenes 2, 12, and 14-17 have interesting different electrochemical properties due to the different co-ligand. The oxidation potentials of complexes 2, 12, 16, and 17 with Cl, NCS, and N(CN)(2) ligands gradually positively shift in the sequence of Cl

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Section: Resultsmentioning

confidence: 91%

“…Roper et al. obtained bromo– and chloro–metallabenzenes from the reactions of [Os{CHCHCHCHC(SMe)}(CO)I(PPh 3 ) 2 ] with Br 2 and PhICl 2 , respectively 14. Jia's bromo–metallabenzyne [Os{CCBrC(CH 3 )CBrCH}Br 2 (PPh 3 ) 2 ] is a related example 22…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh₃ Substituents

Zhang

Lin

et al. 2009

Chemistry A European J

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“…For the synthesis and properties of osmabenzenes, see: Elliott et al (1982Elliott et al ( , 1989; Rickard et al (2000Rickard et al ( , 2001. For a discussion of ring planarity in metallabenzenes, see : Zhu et al (2007).…”

Section: Related Literaturementioning

confidence: 99%

“…To obtain further data relating to the nature of the delocalized bonding in osmabenzenes (Rickard et al, 2000;Rickard et al, 2001) we have obtained the single-crystal X-ray structure of the title complex [Os(C 5 H 4 {SMe-1})Cl(CO)(PPh 3 ) 2 ]. The geometry about…”

Section: S1 Commentmentioning

confidence: 99%

Carbonylchlorido(1-methylsulfanylpenta-1,3-dien-1-yl-5-ylidene)bis(triphenylphosphane)osmium(II)

et al. 2009

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Key indicators: single-crystal X-ray study; T = 203 K; mean (C-C) = 0.005 Å; R factor = 0.022; wR factor = 0.060; data-to-parameter ratio = 17.6.The crystal structure of the title compound, [Os(C 6 H 7 S)Cl-(C 18 H 15 P) 2 (CO)], confirms the formulation as an osmabenzene. There is a slightly distorted octahedral coordination environment at the Os II ion, with the triphenylphosphane ligands mutually trans and the chloride cis to the carbon bearing the -SMe substituent. Within the metallacyclic ring, the C-C distances are appropriate for aromatic bonds and the two Os-C distances are shorter than typical Os-C single bonds. The maximum deviation from the least-squares plane through the osmabenzene ring occurs for the carbon bearing the SMe substituent [0.1037 (18) Å ]. Related literature

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“…respectively, with all PPh 3 and PEt 3 ligands were modeled using PH 3 groups and all substituents on their carbon units were replaced by hydrogen[3,[7][8][9].…”

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confidence: 99%

An investigation of the aromaticity of transition metal heterocyclic complexes by conventional criteria and indices of aromaticity

Huang

Yang

2004

Journal of Organometallic Chemistry

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Electrophilic Aromatic Substitution Reactions of a Metallabenzene: Nitration and Halogenation of the Osmabenzene [Os{C(SMe)CHCHCHCH}I(CO)(PPh3)2]

Cited by 128 publications

References 14 publications

Synthesis, Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh₃ Substituents

Synthesis, Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh₃ Substituents

Carbonylchlorido(1-methylsulfanylpenta-1,3-dien-1-yl-5-ylidene)bis(triphenylphosphane)osmium(II)

An investigation of the aromaticity of transition metal heterocyclic complexes by conventional criteria and indices of aromaticity

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Electrophilic Aromatic Substitution Reactions of a Metallabenzene: Nitration and Halogenation of the Osmabenzene [Os{C(SMe)CHCHCHCH}I(CO)(PPh3)2]

Cited by 128 publications

References 14 publications

Synthesis, Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh3 Substituents

Synthesis, Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh3 Substituents

Carbonylchlorido(1-methylsulfanylpenta-1,3-dien-1-yl-5-ylidene)bis(triphenylphosphane)osmium(II)

An investigation of the aromaticity of transition metal heterocyclic complexes by conventional criteria and indices of aromaticity

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Synthesis, Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh₃ Substituents

Synthesis, Characterization and Electrochemical Properties of Stable Osmabenzenes Containing PPh₃ Substituents