Preparation of bis(η6-2-R-benzo[b]thiophene)-chromium and -molybdenum (R = H, Me, SiMe3) sandwich complexes via metal vapour synthesis. Crystal structure of [Cr(η6-2-Me C8H5S)2]

Burton, Nicolas C.; Geoffrey, F.; Cloke, N.; Hitchcock, Peter B.; Mepsted, Gary O.; Newton, Claire; Patel, Hasmita

doi:10.1016/0022-328x(95)05408-h

Cited by 9 publications

(1 citation statement)

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“…The first reported stable Mo−thiophene complex, (CO) 3 Mo[2,5-(Ph 2 PCH 2 CH 2 ) 2 C 4 H 2 S], exists as a pair of isomers ( mer and fac ) in which the thiophene is part of a chelating ligand that is bound to the Mo center through the phosphine groups and the sulfur. The second, Mo(η 6 -2-MeBT) 2 , is a sandwich complex consisting of a Mo coordinated to two 2-methylbenzothiophene (2-MeBT) ligands through the arene rings in an η 6 fashion. Tungsten−thiophene complexes previously reported include W(PCy 3 ) 2 (CO) 3 (η 1 ( S )-T) and (CO) 5 W(η 1 ( S )-T) .…”

Section: Introductionmentioning

confidence: 99%

Transition Metal Complexes of Chromium, Molybdenum, Tungsten, and Manganese Containing η¹(S)-2,5-Dimethylthiophene, Benzothiophene, and Dibenzothiophene Ligands

et al. 1999

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Ultraviolet photolysis of hexanes solutions containing the complexes M(CO)6 (M = Cr, Mo, W) or CpMn(CO)3 (Cp = η5-C5H5) and excess thiophene (T*) (T* = 2,5-dimethylthiophene (2,5-Me2T), benzothiophene (BT), or dibenzothiophene (DBT)) produces the η1(S)-T* complexes (CO)5M(η1(S)-T*) 1−8 or Cp(CO)2Mn(η1(S)-T*) 9−11, respectively. However, when T* = DBT and M = Mo, a mixture of two products results, which includes (CO)5Mo(η1(S)-DBT), 4a, and the π-complex (CO)3Mo(η6-DBT), 4b, as detected by 1H NMR spectroscopy. Only the complexes (CO)5W(η1(S)-DBT) (1), (CO)5Cr(η1(S)-DBT) (5), and Cp(CO)2Mn(η1(S)-DBT) (9) were sufficiently stable (several days) to be isolated and characterized by elemental analyses. Rates of DBT ligand displacement by CO (1 atm) at room temperature decreased in the order 5 > 1 > 9. Single-crystal, X-ray structural determinations are reported for 1, 5, and 9. The tilt angle (θ) of the DBT ligand in these and related complexes is discussed in terms of π-back-bonding to the DBT ligand.

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Section: Introductionmentioning

confidence: 99%

Transition Metal Complexes of Chromium, Molybdenum, Tungsten, and Manganese Containing η¹(S)-2,5-Dimethylthiophene, Benzothiophene, and Dibenzothiophene Ligands

et al. 1999

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Coordination and Oxidative Addition at a Low-Coordinate Rhodium(I)β-Diiminate Centre

et al. 2002

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The reaction of 14e [LMeRh(coe)] (1; LMe=ArNC(Me)CHC(Me)NAr, Ar=2,6‐Me2C6H3; coe=cis‐cyclooctene) with phenyl halides and thiophenes was studied to assess the competition between σ coordination, arene π coordination and oxidative addition of a C−X bond. Whereas oxidative addition of the C−Cl and C−Br bonds of chlorobenzene and bromobenzene to LMeRh results in the dinuclear species [{LMeRh(Ph)(μ‐X)}2] (X=Cl, Br), fluorobenzene yields the dinuclear inverse sandwich complex [{LMeRh}2(anti‐μ‐η4:η4‐PhF)]. Thiophene undergoes oxidative addition of the C−S bond to give a dinuclear product. The reaction of 1 with dibenzo[b,d]thiophene (dbt) in the ratio 1:2 resulted in the formation of the σ complex [LMeRh(η1‐(S)‐dbt)2], which in solution dissociates into free dbt and a mixture of the mononuclear complex [LMeRh(η4‐(1,2,3,4)‐dbt)] and the dinuclear complex [{LMeRh}2(μ‐η4‐(1,2,3,4):η4‐(6,7,8,9)‐dbt)]. The latter could be obtained selectively by the 2:1 reaction of 1 and dbt. Reaction of 1 with diethyl sulfide produces [LMeRh(Et2S)2], which in the presence of hydrogen loses a diethyl sulfide ligand to give [LMeRh(Et2S)(H2)] and catalyses the hydrogenation of cyclooctene.

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Chromium Compounds without CO or Isocyanides

Carney

2007

Comprehensive Organometallic Chemistry III

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Preparation of bis(η6-2-R-benzo[b]thiophene)-chromium and -molybdenum (R = H, Me, SiMe3) sandwich complexes via metal vapour synthesis. Crystal structure of [Cr(η6-2-Me C8H5S)2]

Cited by 9 publications

References 17 publications

Transition Metal Complexes of Chromium, Molybdenum, Tungsten, and Manganese Containing η¹(S)-2,5-Dimethylthiophene, Benzothiophene, and Dibenzothiophene Ligands

Transition Metal Complexes of Chromium, Molybdenum, Tungsten, and Manganese Containing η¹(S)-2,5-Dimethylthiophene, Benzothiophene, and Dibenzothiophene Ligands

Coordination and Oxidative Addition at a Low-Coordinate Rhodium(I)β-Diiminate Centre

Chromium Compounds without CO or Isocyanides

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Preparation of bis(η6-2-R-benzo[b]thiophene)-chromium and -molybdenum (R = H, Me, SiMe3) sandwich complexes via metal vapour synthesis. Crystal structure of [Cr(η6-2-Me C8H5S)2]

Cited by 9 publications

References 17 publications

Transition Metal Complexes of Chromium, Molybdenum, Tungsten, and Manganese Containing η1(S)-2,5-Dimethylthiophene, Benzothiophene, and Dibenzothiophene Ligands

Transition Metal Complexes of Chromium, Molybdenum, Tungsten, and Manganese Containing η1(S)-2,5-Dimethylthiophene, Benzothiophene, and Dibenzothiophene Ligands

Coordination and Oxidative Addition at a Low-Coordinate Rhodium(I)β-Diiminate Centre

Chromium Compounds without CO or Isocyanides

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Transition Metal Complexes of Chromium, Molybdenum, Tungsten, and Manganese Containing η¹(S)-2,5-Dimethylthiophene, Benzothiophene, and Dibenzothiophene Ligands

Transition Metal Complexes of Chromium, Molybdenum, Tungsten, and Manganese Containing η¹(S)-2,5-Dimethylthiophene, Benzothiophene, and Dibenzothiophene Ligands