Structural studies on polynuclear osmium carbonyl hydrides.  30.  Synthesis, crystal structure, and reactivity of (.mu.-H)Os3(CO)10(.mu.3-CPh)

Yeh, Wen Yann.; Shapley, John R.; Li, Yong Ji

doi:10.1021/om00123a026

Cited by 29 publications

(4 citation statements)

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“…The μ 3 -CNN ligand is linear within experimental error (C(8)−N(1)-N(2) = 177(2) Å) and lies over the triosmium plane. This is analogous to the situation observed for Os 3 (CO) 10 (μ 3 -CH)(μ-H), Os 3 (CO) 10 (μ 3 -CPh)(μ-H)], and Os 3 (CO) 10 (μ 3 -CCHMe 2 )(μ-H) . This is the first structurally characterized example of a μ 3 -CNN ligand C-bonded to a metal.…”

Section: Resultssupporting

confidence: 77%

Carboxylation of a μ₃-Diazo Methylidyne Triosmium Cluster

et al. 2000

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The unsaturated cluster Os 3 (CO) 8 (Ph 2 PCH 2 P(Ph)C 6 H 4 )(µ-H) (1) reacts with CH 2 N 2 at -10 to 25 °C to give two novel compounds Os 3 (CO) 7 (µ 3 -CN 2 )(µ-dppm)(µ-H) 2 (2) and Os 3 (CO) 7 (µ 3 -CCO 2 H)(µ-dppm)(µ-H) 3 (3) characterized by single-crystal X-ray crystallography. Compound 2 is converted to 3 in almost quantitative yield by reaction with CO (atmospheric pressure) and trace H 2 O. The reaction of 2 with molecular hydrogen at atmospheric pressure at 80 °C yields Os 3 (CO) 8 (µ-dppm)(µ-H) 2 (4) and Os 3 (CO) 10 (µ-dppm) (5).

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Section: Resultssupporting

confidence: 77%

Carboxylation of a μ₃-Diazo Methylidyne Triosmium Cluster

et al. 2000

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“…It consists of an Os 3 triangle with two almost equal metal−metal bonds (Os(1)−Os(2) = 2.8915(6) Å, Os(2)−Os(3) = 2.8892(5) Å) and one shorter metal−metal bond (Os(1)−Os(3) = 2.8607(5) Å). The structure is related to that observed for Os 3 (CO) 10 (μ 3 -CR)(μ-H) (R = H, Ph,) with the additional Os−N(1) interaction replacing one radial carbonyl. The 2-methylbenzothiazolide ligand is nearly perpendicular to the plane of the osmium triangle.…”

supporting

confidence: 55%

“…A key feature of 12 is that the μ 3 -CC 7 H 3 (2-CH 3 )NS ligand has significant bonding interactions with all the three osmium atoms, in contrast to the related compounds Os 3 (CO) 10 (μ 3 -CR)(μ 3 -CR). (R = H, Ph, CH 2 CHMe), where the bonding is viewed as semi-triply bridging. The C(9)−C(10) bond vector is nearly perpendicular to the Os 3 plane but is tilted slightly toward Os(3) (∠Os(3)−C(9)−C(10) = 114.3(6)°, ∠Os(2)−C(9)−C(10) = 120.2(7)°, ∠Os(1)−C(9)−C(10) = 145.0(7)°).…”

mentioning

confidence: 99%

Reaction of Os₃(CO)₉(μ₃-η²-C₇H₃(2-CH₃)NS)(μ-H) with Diazomethane. The First Example of a Trimetallic Cluster Containing a μ-Methylidene and a σ-Methyl

et al. 2002

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The electronically unsaturated cluster Os 3 -(CO) 9 (µ 3 -η 2 -C 7 H 3 (2-CH 3 )NS)(µ-H) ( 6) reacts with excess CH 2 N 2 at -10 to +25 °C to give Os 3 (CO) 9), a rare example of a triosmium cluster containing an edge-bridging methylene group and a σ-bound methyl group. On thermolysis in refluxing heptane 9 affords Os 3 (CO) 11) and Os 3 (CO) 8 (µ 3 -η 2 -CC 7 H 3 (2-CH 3 )NS)(µ-H) 3 (12). In contrast, Os 3 (CO) 8 (µ 3 -η 2 -C 7 H 4 NS)(µ-H)( 7) reacts with diazomethane under exactly similar conditions to afford Os 3 (CO) 9 (µ 3 -η 2 -CHC 7 H 4 NS)((µ-H) 2 ( 10), which on thermolysis in refluxing heptane gives Os 3 (CO) 8 (µ 3 -η 2 -CC 7 H 4 NS)(µ 3 -H) 3 ( 13).

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“…The bridging hydride in 17 was not located crystallography but geometrically assigned to bridge the Os(1)−Os(2) edge according to the lengthening of the metal−metal vector. The most interesting feature of the structure of 17 is that the bridging heterocyclic ligand lies over the triosmium plane as reported for (μ-H)Os 3 (CO) 10 (μ 3 -CR) (R = H, Ph, CH 2 CHMe 2 ). − In the complex (μ-H)Os 3 (CO) 10 (μ 3 -CH) the CH ligand is closer to μ 3 and with the three Os−C distances being 2.35(1), 2.01(1), and 2.00(1) Å. In 17 the corresponding osmium−carbon distances are 2.222(13), 2.004(13), and 2.039(13) Å.…”

Section: Resultsmentioning

confidence: 79%

Reactions of Electron-Deficient Triosmium Clusters with Diazomethane: Electrochemical Properties and Computational Studies of Charge Distribution

Mottalib¹,

Begum²,

Abedin³

et al. 2005

Organometallics

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The 46-electron quinoline triosmium clusters (μ-H)Os3(CO)9(μ3-η2-C9H5(R)N) (6, R = 4-CH3; 7, R = H) react with excess CH2N2 at 0 to 25 °C to give (μ-H)2Os3(CO)9(μ3-η2-CHC9H5(R)N) (10, R = 4-CH3; 11, R = H), formed by insertion and subsequent C−H oxidative addition of a CH2 moiety into the ring C(8)−Os bond. In contrast, the related 46-electron quinoxaline compound (μ-H)Os3(CO)9(μ3-η2-C8H5N2) (8) reacts with excess CH2N2 at 0 to 25 °C to give (μ-H)2Os3(CO)9(μ3-η2-CHC8H4(5-CH3)N2) (12), where two CH2 groups have inserted into the C(5)−H bond as well as the C(8)−Os bond, and (μ-H)2Os3(CO)9(μ3-η2-CHC8H5N2) (13), the analogue of 11. The 5-methylquinoxaline compound (μ-H)Os3(CO)9(μ3-η2-C8H4(5-CH3)N2) (9) reacts with diazomethane at 0 to 25 °C to give 12 and Os3(CO)9(μ3-η2-C8H4(5-CH3)N2)(μ-CH2)(CH3) (14), containing an edge-bridging methylene group and a σ-bound methyl group. Thermolysis of 10 and 11 at 98 °C yields (μ-H)3Os3(CO)8(μ3-η2-C(C9H5)(R)N) (15, R = 4-CH3; 16, R = H), (μ-H)Os3(CO)9(μ3-η2-C(C9H5)(R)N) (17, R = 4-CH3; 18, R = H), and (μ-H)Os4(CO)11(μ3-η2-C(C9H5)(R)N) (19, R = 4-CH3; 20, R = H). The trihydrides 15 and 16 are formed by a further C−H activation of the coordinated methylidene group of 10 and 11, respectively. Thermolysis of 10 and 11 in the presence of H2 at 1 atm at 80 °C gives 15 and 16 in high yields. The solid-state structure of 17 reveals that the methylidyne carbon atom has a significant bonding interaction with the osmium atom coordinated to nitrogen. Thermolysis of 12 and 13 at 98 °C gives (μ-H)Os3(CO)9(μ3-η2-CC8H4(R)N2) (21, R = 5-CH3; 22, R = H), whereas a similar thermolysis in the presence of H2 (1 atm) at 80 °C gives (μ-H)3Os3(CO)8(μ3-η2-CC8H4(5-CH3)N2) (23, R = 5-CH3; 24, R = H). The compounds 12, 13, 23, and 24 all show one-electron reversible reductions, and the reduction potentials are similar to previously studied quinoxaline clusters. DFT calculations show that most of the spin density is confined to the heterocyclic ligand, and this explains the similarity between the observed reduction potentials for the products with different bonding modes to cluster but containing the same heterocycle. The qualitative correlation between the calculated natural charges and the distribution of unpaired spin densities in 12 and 13 corroborate this conclusion. The molecular structures of 10, 12, 13, 17, and 20 have been determined by single-crystal X-ray diffraction studies.

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Structural studies on polynuclear osmium carbonyl hydrides. 30. Synthesis, crystal structure, and reactivity of (.mu.-H)Os3(CO)10(.mu.3-CPh)

Cited by 29 publications

References 1 publication

Carboxylation of a μ₃-Diazo Methylidyne Triosmium Cluster

Carboxylation of a μ₃-Diazo Methylidyne Triosmium Cluster

Reaction of Os₃(CO)₉(μ₃-η²-C₇H₃(2-CH₃)NS)(μ-H) with Diazomethane. The First Example of a Trimetallic Cluster Containing a μ-Methylidene and a σ-Methyl

Reactions of Electron-Deficient Triosmium Clusters with Diazomethane: Electrochemical Properties and Computational Studies of Charge Distribution

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Structural studies on polynuclear osmium carbonyl hydrides. 30. Synthesis, crystal structure, and reactivity of (.mu.-H)Os3(CO)10(.mu.3-CPh)

Cited by 29 publications

References 1 publication

Carboxylation of a μ3-Diazo Methylidyne Triosmium Cluster

Carboxylation of a μ3-Diazo Methylidyne Triosmium Cluster

Reaction of Os3(CO)9(μ3-η2-C7H3(2-CH3)NS)(μ-H) with Diazomethane. The First Example of a Trimetallic Cluster Containing a μ-Methylidene and a σ-Methyl

Reactions of Electron-Deficient Triosmium Clusters with Diazomethane: Electrochemical Properties and Computational Studies of Charge Distribution

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Carboxylation of a μ₃-Diazo Methylidyne Triosmium Cluster

Carboxylation of a μ₃-Diazo Methylidyne Triosmium Cluster

Reaction of Os₃(CO)₉(μ₃-η²-C₇H₃(2-CH₃)NS)(μ-H) with Diazomethane. The First Example of a Trimetallic Cluster Containing a μ-Methylidene and a σ-Methyl