Osmabenzenes from the Reactions of HC≡CCH(OH)C≡CH with OsX2(PPh3)3 (X = Cl, Br)

Xia, Haiping; He, Guomei; Zhang, Hong; Wen, Ting Bin; Sung, Ho Yung; Williams, Ian D.; Jia, Guochen

doi:10.1021/ja0486871

Cited by 131 publications

(87 citation statements)

References 15 publications

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“…10 We found that the reaction of OsCl 2 (PPh 3 ) 3 with readily accessible 1,4-pentadiyn-3-ol produced bisphosponium-substituted osmabenzene 3 at room temperature (Scheme 1). When PPh 3 was added to the reaction mixture, the isolated yield of 3 was increased from 44% to 75%.…”

Section: Osmabenzenementioning

confidence: 99%

The Chemistry of Aromatic Osmacycles

et al. 2013

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A romatic compounds, such as benzene and its derivatives, porphyrins, fullerenes, carbon nanotubes, and graphene, have numerous applications in biomedicine, materials science, energy science, and environmental science. Metalla-aromatics are analogues of conventional organic aromatic molecules in which one of the (hydro)carbon segments is formally replaced by an isolobal transition-metal fragment. Researchers have studied these transition-metalcontaining aromatic molecules for the past three decades, particularly the synthesis and reactivity of metallabenzenes. Another focus has been the preparation and characterization of other metalla-aromatics such as metallafurans, metallapyridines, metallabenzynes, and more. Despite significant advances, remaining challenges in this field include the limited number of convenient and versatile synthetic methods to construct stable and fully characterized metalla-aromatics, and the relative shortage of new topologies.To address these challenges, we have developed new methods for preparing metalla-aromatics, especially those possessing new topologies. Our synthetic efforts have led to a large family of closely related metalla-aromatics known as aromatic osmacycles. This Account summarizes the synthesis and reactivity of these compounds, with a focus on features that are different from those of compounds developed by other groups. These osmacycles can be synthesized from simple precursors under mild conditions. Using these efficient methods, we have synthesized aromatic osmacycles such as osmabenzene, osmabenzyne, isoosmabenzene, osmafuran, and osmanaphthalene. Furthermore, these methods have also created a series of new topologies, such as osmabenzothiazole and osmapyridyne. Our studies of the reactivity of these osma-aromatics revealed unprecedented reaction patterns, and we demonstrated the interconversion of several osmacycles.Like other metalla-aromatics, osma-aromatics have spectroscopic features of aromaticity, such as ring planarity and the characteristic bond lengths between a single and double bond, but the osma-aromatics we have prepared also exhibit good stability towards air, water, and heat. Indeed, some seemingly unstable species proved stable, and their stability made it possible to study their optical, electrochemical, and magnetic properties. The stability of these compouds results from their aromaticity and the phosphonium substituents on the aromatic plane: most of our osma-aromatics carry at least one phosphonium group. The phosphonium group offers stability via both electronic and steric mechanisms. The phosphonium acts as an electron reservoir, allowing the circulation of electron pairs along metallacycles and lowering the electron density of the aromatic rings. Meanwhile, the bulky phosphonium groups surrounding the aromatic metallacycle prevent most reactions that could decompose the skeleton.

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Section: Osmabenzenementioning

confidence: 99%

The Chemistry of Aromatic Osmacycles

et al. 2013

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“…A second pathway to stable osmabenzenes was reported by Jia and co-workers in 2004. [35] This group found that reaction of [OsCl 2 (PPh 3 ) 3 ] with 1,4-pentadiyn-3-ol led to the isolation of metallacycle 12, the phosphonium salt of an osmabenzene. The mechanism proposed for formation of this unusual species involves the substitution of a coordinated phosphine ligand with an h 2 -coordinated alkyne to give species 13 (Scheme 3).…”

Section: Osmabenzenesmentioning

confidence: 99%

“…[11] Although a number of metallabenzenes have been synthesized with p donors ortho to the metal fragment, [23,31] iridanaphthalene 107 and iridabenzenes 99, 105, and 115 are the first examples of metalla-aromatic species substituted with electron-withdrawing groups, namely CO 2 Me. Other examples of metallabenzenes bearing electron-withdrawing groups include the phosphonium-substituted osmabenzenes and ruthenabenzenes reported by Jia, [35,62] but these moieties are located on the less influential meta positions.…”

Section: Iridanaphthalenementioning

confidence: 99%

Recent Advances in Metallabenzene Chemistry

2006

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Research into aromatic metallacycles, though discussed in the literature over the last quarter century, has undergone a major expansion since 2000. A wide variety of new metallabenzenes, encompassing new synthetic methods and new metal centers, is now available. New aromatic metallacycle topologies (iridanaphthalene, osmabenzynes) have been isolated and characterized. The first metallabenzene valence isomers (iridabenzvalenes, rhodabenzvalenes) and constitutional isomers (isoosmabenzenes) are now known. This review discusses the synthesis, chemistry, and physical properties of these intriguing aromatic compounds.

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“…Until recently, only two families of discrete metallabenzenes were known, namely Ropers osmabenzenes (e.g., 1) [2] and Bleekes iridabenzenes (e.g., 2); [3] nonetheless, all investigations into both families originated from compounds 1 and 2, respectively. Very recent work on osmabenzenes [4] and irida-aromatic compounds [5] has provided a few additional examples; however, the generality of these methods has yet to be determined. Therein lies a key difficulty within this field of research: lack of versatile synthetic routes has meant that detailed, fundamental study of metallabenzenes has been problematic.…”

Section: Introductionmentioning

confidence: 99%

Regioselective Formation of β‐Alkyl‐α‐phenyliridabenzenes via Unsymmetrical 3‐Vinylcyclopropenes: Probing Steric and Electronic Influences by Varying the Alkyl Ring Substituent

Weakley

Haley

2005

Chemistry A European J

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The synthesis of unsymmetrical (Z)-1-alkyl-3-(2-iodovinyl)-2-phenyl-1-cyclopropenes (R=Me (8 a), Et (8 b), iPr (8 c), and tBu (8 d)) and their reactions with Vaska's complex [Ir(CO)Cl(PPh3)2] and its trimethylphosphine analogue [Ir(CO)Cl(PMe3)2] were investigated. Iridabenzvalene (13/20), iridabenzene (14/21), and/or eta(5)-cyclopentadienyliridium complexes (15/22) were obtained in modest yields and were fully characterized by spectroscopic means. X-ray structural data was secured for iridabenzvalene 13 d and iridabenzenes 14 a,b,d. Whereas iridabenzenes 14 a-c were stable at 75 degrees C for 48 h, 14 d, which possesses a bulky tBu group, rearranged cleanly to cyclopentadienyliridium 15 d at 50 degrees C over 15 h and displayed first-order kinetics. The influence of the alkyl substituent on the mechanisms of iridacycle generation, isomerization, and iridabenzene regioselectivity is discussed.

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Osmabenzenes from the Reactions of HC≡CCH(OH)C≡CH with OsX₂(PPh₃)₃ (X = Cl, Br)

Abstract: Treatment of OsX2(PPh3)3 (X = Cl, Br) with HCCCH(OH)CCH in THF produces OsX2(CH=C(PPh3)CH(OH)CCH)(PPh3)2, which reacts with PPh3 to give osmabenzenes [Os(CHC(PPh3)CHC(PPh3)CH)X2(PPh3)2]+.

Cited by 131 publications

References 15 publications

The Chemistry of Aromatic Osmacycles

The Chemistry of Aromatic Osmacycles

Recent Advances in Metallabenzene Chemistry

Regioselective Formation of β‐Alkyl‐α‐phenyliridabenzenes via Unsymmetrical 3‐Vinylcyclopropenes: Probing Steric and Electronic Influences by Varying the Alkyl Ring Substituent

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