Synthesis, Characterization, and Molecular Structure of the First closo-Hydrido Complexes of Osmium with Carborane Ligands:  closo-3,3-(PPh3)2-3-H-3-Cl-3,1,2-OsC2B9H11 and closo-3,3-(PPh3)2-3,3-H2-1,2-Me2-3,1,2-OsC2B9H9

Chizhevsky, I. T.; Petrovskii, P. V.; Sorokin, P.; Bregadze, V. I.; Dolgushin, Fedor M.; Yanovsky, A. I.; Struchkov, Yuri T.; Demonceau, Albert; Noels, Alfred F.

doi:10.1021/om950967p

Cited by 17 publications

(3 citation statements)

References 34 publications

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“…can be successfully substituted for [( 4 -COD)Rh(acac)] in the room-temperature synthesis of complex 67a in benzene. In this case, however, the known species [3,3-(PPh 3 ) 3 -3-Cl-3-H-3,1,2-closo-OsC 2 B 9 H 12 ] [55] was formed as a by-product in small amounts due apparently to the mild exo-nido-to-closo conversion of the starting complex 66.…”

Section: Homo-and Heterometallic Exo-closo-bimetallacarboranesmentioning

confidence: 84%

Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

Chizhevsky

2007

Coordination Chemistry Reviews

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Section: Homo-and Heterometallic Exo-closo-bimetallacarboranesmentioning

confidence: 84%

Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

Chizhevsky

2007

Coordination Chemistry Reviews

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“…ELO data for cis ‐[3,3‐(CO) 2 ‐3,3‐(Cl) 2 ‐3,1,2‐ closo ‐ReC 2 B 9 H 11 ] – ( FINWIJ ), cis ‐[3,3‐(CO) 2 ‐3,3‐(SPh) 2 ‐3,1,2‐ closo ‐MoC 2 B 9 H 11 ] 2– ( TOJREP ), trans ‐[3,3‐(PPh 3 ) 2 ‐3‐H‐3‐Cl‐3,1,2‐ closo ‐OsC 2 B 9 H 11 ] ( TEXYUQ ), and trans ‐[3,3‐(PPh 3 ) 2 ‐3‐H‐3‐Cl‐3,1,2‐ closo ‐RuC 2 B 9 H 11 ] ( QEXWAS ) are presented in Table . The data for FINWIJ and TOJREP clearly demonstrate that CO has a stronger trans influence than the ligands Cl and SPh, respectively, since the cis ‐CO ligands adopt positions defined by high | θ | values.…”

Section: Resultsmentioning

confidence: 99%

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

et al. 2017

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Analysis of the literature structures [(CO)(PPh3)2MC2B9H11] and [(CO)2(PPh3)MC2B9H11] suggests that in [L3MC2B9H11] metallacarboranes the trans influence of CO is greater than that of PPh3. Extending this study to the [L4MC2B9H11] system the new molybdacarboranes [3,3,3‐(CO)3‐3‐PPh3‐3,1,2‐closo‐MoC2B9H11] (2), [1,2‐Me2‐3,3,3‐(CO)3‐3‐PPh3‐3,1,2‐closo‐MoC2B9H9] (3) and trans‐[3,3‐(CO)2‐3,3‐(PPh3)2‐3,1,2‐closo‐MoC2B9H11] (4) were prepared and fully characterised. Consideration of the exopolyhedral ligand orientations (ELO) in 2 confirms that, in terms of trans influence, CO > PPh3 in [L4MC2B9H11] also. The ELO is effectively reversed in 3 through intramolecular steric crowding between the cage CH3 groups and the PPh3 ligand. The dicarbonylbis(triphenylphosphine) compound 4 has effective Cs symmetry with one CO ligand trans and the other CO ligand cis to the cage C–C connectivity. Unexpectedly the Mo–CO bond lengths are equal. DFT calculations on 4 reproduce this unusual result, but suggest that in the less‐crowded PH3 analogue, the Mo–CO bond length trans to cage C would be about 0.2 Å shorter than that trans to cage B. To test this prediction, the analogous PEt3 complex was prepared as cis and trans structural isomers 5 and 6. The cis isomer 5 is quantitatively converted into the trans isomer 6 when heated to reflux in THF. In 6 the Mo–CO bond more trans to cage C is about 0.2 Å shorter than that which is more trans to cage B, in line with the DFT prediction.

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“…Since little attention has been given in the literature to closo -hydrido-osmacarborane clusters and no examples with the carbons-apart { nido -7,9-C 2 B 9 } ligands were reported, a single-crystal X-ray diffraction study of 13 has been undertaken. This study confirmed the closo structure of 13 and made clear some details of its cluster geometry and the arrangement of ligands at the metal vertex.…”

Section: Resultsmentioning

confidence: 99%

Stable exo-nido-Metallacarboranes (M = Os^IV) that Incorporate meta-Carborane-Based Dicarbollide Ligands

et al. 2007

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Reactions of the [K]+ salts of the [nido-7,9-C2B9H12]- anion (2) and its C-phenylated derivative [7-Ph-nido-7,9-C2B9H11]- (4) with [OsCl2(PPh3)3] (3) proceed in benzene at ambient temperature with the formation of 16-electron chlorohydrido-Os(IV) exo-nido complexes, [exo-nido-10,11-{(Ph3P)2OsHCl}-10,11-(mu-H)2-7-R-7,9-C2B9H8] (5: R = H; 6: R = Ph), along with the small amounts of the charge-compensated nido-carboranes [nido-7,9-C2B9H11PPh3] (7) and [7-Ph-nido-7,9-C2B9H10PPh3] (8) as byproducts. However, when carried out under mild heating in ethanol, the reaction of 2 with 3 selectively afforded a 16-electron dihydrido-Os(IV) exo-nido complex [exo-nido-10,11-{(Ph3P)2OsH2}-10,11-(mu-H)2-7,9-C2B9H9] (9). Structures of both complexes 5 and 9 have been confirmed by single-crystal X-ray diffraction studies, which revealed that nido-carboranes in these species function as a bidentate dicarbollide ligands [7-R-nido-7,9-C2B9H10]2- linked to the Os(IV) center via two B-H...Os bonds involving adjacent B-H vertices in the upper CBCBB belt of the carborane cage. Thus, compounds 5 and 9 represent the first structurally characterized exo-nido-metallacarboranes based on meta-dicarbollide-type ligands. Variable-temperature 1H and 31P{1H} NMR experiments indicate that complex 9 is fluxional in solution and shows an unusual exchange between terminal Os-(H)2 and bridging {B-H}2...Os hydrogen atoms. Upon heating in d8-THF at 65 degrees C, complex 9 converts irreversibly to its closo isomer [2,2-(PPh3)2-2,2-H2-closo-2,1,7-OsC2B9H11] (13), which could thus be obtained as a pure crystalline solid. The structure of 13 has been established on the basis of analytical and multinuclear NMR data and a single-crystal X-ray diffraction study.

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Synthesis, Characterization, and Molecular Structure of the First closo-Hydrido Complexes of Osmium with Carborane Ligands: closo-3,3-(PPh₃)₂-3-H-3-Cl-3,1,2-OsC₂B₉H₁₁ and closo-3,3-(PPh₃)₂-3,3-H₂-1,2-Me₂-3,1,2-OsC₂B₉H₉

Cited by 17 publications

References 34 publications

Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

Stable exo-nido-Metallacarboranes (M = Os^IV) that Incorporate meta-Carborane-Based Dicarbollide Ligands

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Synthesis, Characterization, and Molecular Structure of the First closo-Hydrido Complexes of Osmium with Carborane Ligands: closo-3,3-(PPh3)2-3-H-3-Cl-3,1,2-OsC2B9H11 and closo-3,3-(PPh3)2-3,3-H2-1,2-Me2-3,1,2-OsC2B9H9

Cited by 17 publications

References 34 publications

Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

Balancing Steric and Electronic Effects in Carbonyl–Phosphine Molybdacarboranes

Stable exo-nido-Metallacarboranes (M = OsIV) that Incorporate meta-Carborane-Based Dicarbollide Ligands

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Synthesis, Characterization, and Molecular Structure of the First closo-Hydrido Complexes of Osmium with Carborane Ligands: closo-3,3-(PPh₃)₂-3-H-3-Cl-3,1,2-OsC₂B₉H₁₁ and closo-3,3-(PPh₃)₂-3,3-H₂-1,2-Me₂-3,1,2-OsC₂B₉H₉

Stable exo-nido-Metallacarboranes (M = Os^IV) that Incorporate meta-Carborane-Based Dicarbollide Ligands