Mixed μ-phosphido or μ-thiolato μ-halo-dimolybdenum(III) compounds [Mo2Cp2(μ-SMe)2(μ-X)(μ-Y)] (X=PPh2, Y=Cl; X=SCH3, Y=Br, I): Electrochemical and structural comparisons – The X-ray structure of [{Mo2Cp2Br(μ-O)(μ-SMe)2}2(μ-MoO4)]

Roy, Christine Le; Pétillon, François Y.; Muir, Kenneth W.; Schollhammer, Philippe; Talarmin, Jean

doi:10.1016/j.jorganchem.2005.10.033

Cited by 7 publications

(3 citation statements)

References 24 publications

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“…The Mo−O distances (1.919(12) Å) in 7′ compared to the Mo−S(sulfido) bond lengths (2.347(6) Å) in 6′ are strong indirect proof that 7′ contains a μ-oxo ligand and not a μ-sulfido one. These distances are close to those found in related μ-oxomolybdenum complexes, e.g [Mo 2 Cp 2 *Br 2 (μ-SMe)(μ-Br)(μ-O)] (average 1.910 Å), [{Mo 2 Cp 2 Br(μ-O)(μ-SMe) 2 } 2 (μ-MoO 4 )] (average 1.935 Å), and [(MoCpCl) 2 (μ-Cl)(μ-CO 3 H)(μ-O)]…”

Section: Resultssupporting

confidence: 82%

“…The superposition of the four equally likely Mo−S and Mo−S−C orientations displays a structure which is symmetrical related to the Cp mirror (Mo, Mo i , C1, C1 i ) and quasi-symmetrical related to the pseudobinary (C4−C4 ii ) axis. The cation of 6′ is structurally related to the quadruply bridged dimolybdenum species [Mo 2 Cp 2 (μ-SMe) 3 (μ-X)] (X = Cl, Br, I, SMe), containing three-electron-donor halide or pseudohalide. The cation consists of two CpMo fragments which are directly connected by a Mo−Mo bond of 2.5304(7) Å in addition to being bridged by three thiolates and one sulfido ligand.…”

Section: Resultsmentioning

confidence: 99%

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Carbon−Sulfur and Carbon−Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo₂Cp₂(μ-SMe)₃(MeCN)₂]⁺

et al. 2009

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Reactions of the trithiolato-bridged complex [Mo 2 Cp 2 (μ-SMe) 3 (MeCN) 2 ](BF 4 ) (1) with acyclic (e.g., Et 2 S) or cyclic (e.g., thiirane, thietane, tetrahydrothiophene, 1,4-dithiane, and 1,4-thioxane) thioethers and chalcogenophenes (benzothiophene, benzoselenophene, and dibenzothiophene) in dihaloalkanes led to either the thioether-and halide-bridged compounds [Mo 2 Cp 2 (μ-SMe) 2 (μ-SRR 0 )(μ-X)](BF 4 ) (R=R 0 =Et, X=Cl (3); RR 0 =C 4 H 8 , X=Cl (10), X=Br (11) ; RR 0 =C 4 H 8 O, X = Cl ( 14)), and dithioether-and chloro-bridged derivatives [Mo 2 Cp 2 (μ-SMe) 2 (μ-Cl){μ-κ 1 (S), κ 1 (S)-(SR 00x (CH 2 ) n SR 00x }](BF 4 ) (x=1, R 00 =Me, n=1 (4); x=0, n=4 (13)) or the μ-sulfido complex [Mo 2 Cp 2 (μ-SMe) 3 (μ-S)](BF 4 ) (6) and the methyl 1,3-propylthiolate thioether-bridged compound [Mo 2 Cp 2 (μ-SMe) 2 {μ-κ 2 (S),κ 2 (S)-S(CH 2 ) 3 SMe}](BF 4 ) (8), according to the structural features of the organic sulfur reagents. Ring-opening reaction through the cleavage of C-S bonds occurred when small-ring thioethers (e.g., thiirane and thietane) are used as reagents, whereas facile C-X (X = Cl, Br) bond cleavage was observed for other sulfur molecules. Some reactions that were conducted in chlorocarbon solvents (e.g., CH 2 Cl 2 , (CH 2 ) 2 Cl 2 ) gave rise to the formation of the oxo-bridged complex [Mo 2 Cp 2 (μ-SMe) 3 (μ-O)](BF 4 ) (7) as a byproduct with moderate yields. All new complexes have been characterized by elemental analyses and spectroscopic methods, supplemented for the tetraphenylborate or hexafluorophosphate salts of 4, 6-8, 10, and 13 by X-ray diffraction.

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Section: Resultssupporting

confidence: 82%

Section: Resultsmentioning

confidence: 99%

Carbon−Sulfur and Carbon−Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo₂Cp₂(μ-SMe)₃(MeCN)₂]⁺

et al. 2009

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“…The relatively short Mo−Mo distance of 2.5909(11) Å and acute Mo−X−Mo (X = Cl, S) bridging angles (62.21(6)−64.29(6)°) are consistent with the presence of direct metal−metal bonding . The Mo−Mo bond length of 2.5909(11) Å in the unit cell is typical of single (Cp)Mo(III)−Mo(III)(Cp) bonds in related quadruply bridged species containing three-electron-donor halide or pseudohalide (Y) ligands (Y = SR, Cl, Br, I, Cl/SR, , Br/SR, I/SR, SR/PR 2 , Cl/PR 2 , , SR/NNR, SR/NCR 2 , SR/CCR, SR/Cl/PR 2 , and SR/PR 2 /NCR 2 ), which lie in the range 2.574(1)−2.708(3) Å. The Mo−Mo bond length in 3 is also very similar to that in 2 (Mo−Mo = 2.601(1) Å), suggesting that replacement of one bridging SMe group by a chlorine has little influence on the molybdenum−molybdenum bonding.…”

Section: Resultsmentioning

confidence: 99%

Thermal Generation and Structures of the Unsaturated Doubly Bridged Complex [Mo₂Cp₂Cl₂(μ-SMe)₂] and Its Quadruply Bridged Isomer [Mo₂Cp₂(μ-Cl)₂(μ-SMe)₂]

et al. 2011

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The doubly and quadruply bridged isomers [Mo2Cp2Cl2(μ-SMe)2] (4) and [Mo2Cp2(μ-Cl)2(μ-SMe)2] (3) have been obtained as side-products when the dicarbonyl precursor [Mo2Cp2(CO)2(μ-SMe)3]Cl (1) is warmed in toluene solution, the main product being the tris-thiolato-bridged compound [Mo2Cp2(μ-Cl)(μ-SMe)3] (2). Complex 4 is stable at room temperature but can be transformed into 3 at elevated temperatures. 3 and 4 have been crystallographically characterized, and both contain equivalent molybdenum centers. The Mo−Mo separations of 2.5909(11) and 2.4507(2) Å in 3(syn) and 4 are consistent with single and triple Mo−Mo bonds, respectively.

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Solvothermal Treatment of Triangular Molybdenum(IV) Oxo Species – A New Approach for the Synthesis of New Molybdenum Oxo Clusters

Zhao

2011

Eur J Inorg Chem

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Mixed μ-phosphido or μ-thiolato μ-halo-dimolybdenum(III) compounds [Mo2Cp2(μ-SMe)2(μ-X)(μ-Y)] (X=PPh2, Y=Cl; X=SCH3, Y=Br, I): Electrochemical and structural comparisons – The X-ray structure of [{Mo2Cp2Br(μ-O)(μ-SMe)2}2(μ-MoO4)]

Cited by 7 publications

References 24 publications

Carbon−Sulfur and Carbon−Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo₂Cp₂(μ-SMe)₃(MeCN)₂]⁺

Carbon−Sulfur and Carbon−Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo₂Cp₂(μ-SMe)₃(MeCN)₂]⁺

Thermal Generation and Structures of the Unsaturated Doubly Bridged Complex [Mo₂Cp₂Cl₂(μ-SMe)₂] and Its Quadruply Bridged Isomer [Mo₂Cp₂(μ-Cl)₂(μ-SMe)₂]

Solvothermal Treatment of Triangular Molybdenum(IV) Oxo Species – A New Approach for the Synthesis of New Molybdenum Oxo Clusters

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Mixed μ-phosphido or μ-thiolato μ-halo-dimolybdenum(III) compounds [Mo2Cp2(μ-SMe)2(μ-X)(μ-Y)] (X=PPh2, Y=Cl; X=SCH3, Y=Br, I): Electrochemical and structural comparisons – The X-ray structure of [{Mo2Cp2Br(μ-O)(μ-SMe)2}2(μ-MoO4)]

Cited by 7 publications

References 24 publications

Carbon−Sulfur and Carbon−Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo2Cp2(μ-SMe)3(MeCN)2]+

Carbon−Sulfur and Carbon−Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo2Cp2(μ-SMe)3(MeCN)2]+

Thermal Generation and Structures of the Unsaturated Doubly Bridged Complex [Mo2Cp2Cl2(μ-SMe)2] and Its Quadruply Bridged Isomer [Mo2Cp2(μ-Cl)2(μ-SMe)2]

Solvothermal Treatment of Triangular Molybdenum(IV) Oxo Species – A New Approach for the Synthesis of New Molybdenum Oxo Clusters

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Carbon−Sulfur and Carbon−Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo₂Cp₂(μ-SMe)₃(MeCN)₂]⁺

Carbon−Sulfur and Carbon−Halogen Bond Cleavage of Acyclic or Cyclic Thioethers, Thiophenes, and Dihaloalkanes with the Trithiolato-Bridged Cation [Mo₂Cp₂(μ-SMe)₃(MeCN)₂]⁺

Thermal Generation and Structures of the Unsaturated Doubly Bridged Complex [Mo₂Cp₂Cl₂(μ-SMe)₂] and Its Quadruply Bridged Isomer [Mo₂Cp₂(μ-Cl)₂(μ-SMe)₂]