Reactivity of Triosmium Carbonyl Clusters with 1,8-Diaminonaphthalene − Synthesis and Structural Characterization of Amido, Diamido, and C-Metalated Trinuclear Derivatives

Cabeza, Javier??A.; Nöth, Heinrich; Rosales-Hoz, María??de??Jesús; Sánchez-Cabrera, Gloria

doi:10.1002/1099-0682(200011)2000:11<2327::aid-ejic2327>3.3.co;2-y

Cited by 4 publications

(6 citation statements)

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“…Following the above-mentioned concept we envisioned a Suzuki cross-coupling [6] of the building blocks 2 and 3 as a possible key step for the construction of the carbon skeleton of 1 (Scheme 1). While the vinyl boronic acid 2 was to be derived from the fragements 4 and 5 by a stereoselective aldol reaction, [7] the synthesis of bithiazole 3 was planned starting from 2,4-dibromothiazole (6). Initial attempts aimed at a cross-coupling of isopropyl zinc chloride with 2,4-dibromothiazole (6) were not promising and delivered only minor quantities of the desired product 7.…”

Section: Methodsmentioning

confidence: 99%

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Transition Metal Complexes with the Proton Sponge 4,9-Dichloroquino[7,8-h]quinoline: Highly Twisted Aromatic Systems and an Extreme “Out-of-Plane” Position of the Coordinated Transition Metal Atom

Wüstefeld

Kaska

Stucky

et al. 2001

Angew. Chem. Int. Ed.

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Section: Methodsmentioning

confidence: 99%

“…[6] Although 1,8-diaminonaphthalene [7,8] is not a proton sponge a few transition metal complexes are known.…”

Section: Dedicated To Professor Heinz a Staab On The Occasion Of Hismentioning

confidence: 99%

Transition Metal Complexes with the Proton Sponge 4,9-Dichloroquino[7,8-h]quinoline: Highly Twisted Aromatic Systems and an Extreme “Out-of-Plane” Position of the Coordinated Transition Metal Atom

Wüstefeld

Kaska

Stucky

et al. 2001

Angew. Chem. Int. Ed.

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“…Naphthyl atom C(1) is bonded to both osmium atoms (Os1–C1 = 2.313(11) Å and Os2–C1 = 2.332(11) Å). Interestingly, naphthyl atom C(6) is also bonded to Os(2) (Os2–C6 = 2.544(10) Å), although the distance is slightly longer. , As a result, the plane of the planar C 10 ring is not perpendicular to the Os 3 triangle but is 49.27(0.27)° from the Os 3 plane. The C1–C6 distance is 1.380(14) Å.…”

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confidence: 99%

Synthesis and Transformations of Triosmium Carbonyl Cluster Complexes Containing Bridging Aryl Ligands

2012

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The reaction of Os 3 (CO) 10 (NCMe) 2 (1) with C 6 H 5 Au(PPh 3 ) has yielded the complex Os 3 (CO) 10 (μ,η 1 -C 6 H 5 )(μ-AuPPh 3 ) (2), which contains an bridging η 1 -phenyl ligand and a Au(PPh 3 ) group that bridges the same unsaturated Os−Os bond in the 46-electron cluster complex. When it was heated to reflux in an octane solution (125 °C), compound 2 was decarbonylated and converted to the complex Os 3 (CO) 9 (μ 3 -C 6 H 4 )(μ-AuPPh 3 )(μ-H) (3), which contains a triply bridging benzyne ligand by a CH cleavage on the bridging phenyl ring. The reaction of Os 3 (CO) 10 (NCMe) 2 with (1-C 10 H 7 )Au(PPh 3 ) (1-C 10 H 7 = 1-naphthyl) yielded the complex Os 3 (CO) 10 (μ-2-C 10 H 7 )(μ-AuPPh 3 ) (4), which exists as two isomeric forms in the solid state. A 1,2-hydrogen shift in the naphthyl ligand occurred in the formation of 4. The green isomer 4a is structurally similar to 2 and contains a bridging η 1 -2-naphthyl ligand and a bridging Au(PPh 3 ) group and is electronically unsaturated overall. The pink isomer 4b contains a bridging η 2 -2naphthyl ligand and a bridging Au(PPh 3 ) group and is electronically saturated. The pink isomer is found in hexane solution and was converted to the complex Os 3 (CO) 9 (μ 3 -C 10 H 6 )(μ-AuPPh 3 )(μ-H) (5) when heated to reflux in octane (125 °C) for 30 min. Compound 5 contains a triply bridging 1,2-naphthyne ligand.

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“…The Os−N (amido) distances in 3a and 3b are also longer than the Os−N (imido) distance of 1.775 Å in [Os VI (4-Cl-TPP)(N t Bu) 2 ] 13b [H 2 (4-Cl-TPP) = meso -tetrakis( p -chlorophenyl)porphyrin] and 1.749(7) Å in [Os V (Tp)(Cl) 2 (NH)] . They are, however, shorter than the Os−N (amido) distance in [Os 3 (μ-dan)(CO) 10 ] [2.165 Å; H 2 (dan) = 1,8-diaminonaphthalene] . The average Os−Cl distances in 6 and 8 [2.333(8)−2.349(1) Å] are similar, but they are slightly shorter than related values in [Os IV (NPPh 3 )(salophen)(Cl)] [H 2 (salopen) = N , N ‘ -bis(salicylidene) o -phenylenediamine; 2.424(5) Å] 1c and [Os(bpb)(PPh 3 )(Cl)] [H 2 (bpb) = N , N ‘ -bis(2‘-pyridinecarboxamide)-1,2-benzene; 2.410(4) Å] .…”

Section: Resultsmentioning

confidence: 80%

Chiral Osmium Complexes with Sterically Bulky Schiff-Base Ligands. Crystal Structures of Os(IV) Derivatives and the Reactivity and Catalytic Cyclopropanation of Alkenes with EDA

et al. 2005

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The syntheses and reactivities of sterically encumbered trans-dioxoosmium(VI) complexes containing Schiff-base ligands bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamine (H2tBu-salch) and bis(3,5-dibromosalicylidene)-1,2-cyclohexane-diamine (H2Br-salch) are described. Reactions of [Os(VI)tBu-salch)O2] (1a) and [Os(VI)(Br-salch)O2] (1b) with PPh(3), p-X-arylamines (X = NO2, CN), N2H4 x H2O, Ph2NNH2, SOCl2, CF3CO2H, Br2, and I2 under reducing conditions gave [Os(II)(Br-salch)(OPPh3)2] (2), [Os(IV)(Br-salch)(p-X-C6H4NH)2] (3), [mu-O-{Os(IV)(tBu-salch)(p-NO2C6H4NH)}2] (4), [Os(II)(Br-salch)(N2)(H2O)] (5), [Os(IV)(tBu-salch)(OH)(Cl)] (6), [Os(IV)(tBu-salch)(OH)2] (7), [Os(IV)(tBu-salch)Cl2] (8), [Os(IV)(tBu-salch)(CF3CO2)2] (9), [Os(IV)(tBu-salch)Br2] (10), and [Os(IV)(tBu-salch)I2] (11), respectively. X-ray crystal structure determinations of [Os(IV)(Br-salch)(p-NO2C6H4NH)2] (3a), [Os(IV)(Br-salch)(p-CNC6H4NH)2] (3b), 6, 8, 9, and 11 reveal the Os-N(amido) distances to be 1.965(4)-1.995(1) A for the bis(amido) complexes, Os-Cl distances of 2.333(8)-2.3495(1) A for 6 and 8, Os-O(CF3CO2) distances of 2.025(6)-2.041(6) A for 9, and Os-I distances of 2.6884(6)-2.6970(6) A for 11. Upon UV irradiation, (1S,2S)-(1a) reacted with aryl-substituted alkenes to give the corresponding epoxides in moderate yields, albeit with no enantioselectivity. The (1R,2R)-6 catalyzed cyclopropanation of a series of substituted styrenes exhibited moderate to good enantioselectivity (up to 79% ee) and moderate trans selectivity.

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Reactivity of Triosmium Carbonyl Clusters with 1,8-Diaminonaphthalene − Synthesis and Structural Characterization of Amido, Diamido, and C-Metalated Trinuclear Derivatives

Cited by 4 publications

References 4 publications

Transition Metal Complexes with the Proton Sponge 4,9-Dichloroquino[7,8-h]quinoline: Highly Twisted Aromatic Systems and an Extreme “Out-of-Plane” Position of the Coordinated Transition Metal Atom

Transition Metal Complexes with the Proton Sponge 4,9-Dichloroquino[7,8-h]quinoline: Highly Twisted Aromatic Systems and an Extreme “Out-of-Plane” Position of the Coordinated Transition Metal Atom

Synthesis and Transformations of Triosmium Carbonyl Cluster Complexes Containing Bridging Aryl Ligands

Chiral Osmium Complexes with Sterically Bulky Schiff-Base Ligands. Crystal Structures of Os(IV) Derivatives and the Reactivity and Catalytic Cyclopropanation of Alkenes with EDA

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