Photochemisches verhalten von tricarbonyl-η5:1-(2-cyclopentadiendiyl)ethyl-molybdän und -wolfram gegenüber cyclischen dienen

Kreiter, Cornelius G.; Wenz, Martin; Bell, Peter

doi:10.1016/0022-328x(90)87233-4

Cited by 7 publications

(4 citation statements)

References 13 publications

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“…These parameters are similar to those previously obtained for the unsubstituted analogue [(Ind)(η 5 -C 5 H 4 CH 2 -η 1 -CH 2 )Mo(CO)][BF 4 ] (Cg(Ind)−Mo−Cg(Cp) = 145.43(2), 145.43(2)°; C(CO)−Mo−C(CH 2 ) = 88.5(2), 92.4(2)°) . The distance between the molybdenum atom and the centroid of the cyclopentadienyl ligand (1.946(1)−1.952(3) Å) and the bond lengths Mo−C(CH 2 ) (2.280(3)−2.297(6) Å) are in line with those for other molybdenum(IV) compounds containing an η 5 :η 1 -cyclopentadienidoethyl ligand (Mo−Cg(Cp) = 1.934−1.983(4) Å, Mo−C(CH 2 ) = 2.268(5)−2.281(7) Å). , The bond lengths Mo−C(CO) were found to be 1.990(3) Å for 16a(A) , 2.001(3) Å for 16a(B) , and 1.999(6) Å for 18 . The distances between molybdenum and the five-membered ring of indenyl are 2.0152(13) Å for 16a(A) , 2.0063(12) Å for 16a(B) , and 2.009(2) Å for 18 .…”

Section: Resultssupporting

confidence: 77%

Reaction of Spiro[2.4]hepta-4,6-diene with Molybdenum(II) Indenyl Compounds: Effects of Substitution in the Indenyl Ligand

et al. 2011

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The series of molybdenum indenyl compounds [(Ind 0 )Mo(CO) 2 (NCMe) 2 ] [BF 4 ] was prepared, and their reactivity toward spiro[2.4]hepta-4,6-diene was studied. It was observed that the spiro-[2.4]hepta-4,6-diene ring opening could be blocked through substitution in the indenyl ring. Hence, the 2-substituted compound [(η 5 -C 9 H 6 Me)Mo(CO) 2 (NCMe) 2 ][BF 4 ] and 1,3-disubstituted compound [(η 5 -C 9 H 5 t Bu 2 )Mo(CO) 2 (NCMe) 2 ][BF 4 ] do not produce the usual ansa-compounds but the compounds with η 4 -bonded spiro[2.4]hepta-4,6-diene [(Ind 0 )(η 4 -C 5 H 4 (CH 2 ) 2 )Mo(CO) 2 ][BF 4 ]. The use of 1-substituted compounds [(η 5 -C 9 H 6 R)Mo(CO) 2 (NCMe) 2 ][BF 4 ] (R = Ph, t Bu) or compounds with less sterically demanding substituents in the 1,3-positions [(η 5 -C 9 H 5 Ph 2 )Mo(CO) 2 (NCMe) 2 ]-[BF 4 ] does not block the ring-opening reaction. These compounds give ansa-molybdenocenes [(Ind 0 )(η 5 -C 5 H 4 CH 2 -η 1 -CH 2 )Mo(CO)][BF 4 ] in a manner similar to that for the unsubstituted analogue. The reaction products were characterized by NMR and IR spectroscopy. Structures of [(η 5 -C 9 H 5 Ph 2 )Mo(η 3 -C 3 H 5 )(CO) 2 ], [(η 5 -C 9 H 6 Ph)(η 5 -C 5 H 4 CH 2 -η 1 -CH 2 )Mo(CO)][BF 4 ], and [(η 5 -C 9 H 5 Ph 2 )(η 5 -C 5 H 4 CH 2 -η 1 -CH 2 )Mo(CO)][BF 4 ] were determined by single-crystal X-ray analysis.

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Section: Resultssupporting

confidence: 77%

Reaction of Spiro[2.4]hepta-4,6-diene with Molybdenum(II) Indenyl Compounds: Effects of Substitution in the Indenyl Ligand

et al. 2011

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“…Thermolysis of (η 5 -C 5 Me 5 )W(σ-alkyl)(π-allyl) complexes generates 16-electron η 2 -diene intermediates that can be trapped as their 18-electron PMe 3 adducts . Photolysis of tungsten, , molybdenum, , rhenium, and cobalt carbonyl compounds in the presence of diene also forms η 2 -diene compounds. Similarly, treatment of molybdenum η 4 -diene compounds with a tertiary phosphine or CO forms the corresponding molybdenum η 2 -diene compound .…”

Section: Resultsmentioning

confidence: 99%

Syntheses, X-ray Crystal Structures, and Solution Behavior of Cationic, Two-Coordinate Gold(I) η²-Diene Complexes

Brooner

Widenhoefer

2011

Organometallics

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A family of cationic gold π-diene complexes of the form {[P(t-Bu) 2 o-biphenyl]Au(η 2 -diene)} þ SbF 6 À were isolated in >80% yield from reaction of various dienes with a mixture of [P(t-Bu) 2 o-biphenyl]AuCl and AgSbF 6 and were characterized by spectroscopy and, in four cases, by X-ray crystallography. Solution and solid-state analysis of these complexes established selective binding of gold to the less substituted CdC bond of the diene in the case of dienes that possessed differentially substituted CdC bonds. 13 C NMR analysis and evaluation of the relative binding affinities of substituted dienes point to a bonding model in which the goldÀalkene interaction is stabilized via donation of electron density from the uncomplexed CdC bond to the complexed CdC bond of the diene. Variable-temperature NMR analysis of gold π-diene complexes revealed fluxional behavior consistent with facile (ΔG ‡ = 9.6À11.9 kcal mol À1 ) intramolecular exchange of the complexed and uncomplexed CdC bonds of the diene ligand.

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“…[15] The resulting products are functionalized equally on both rings. The problem of functionalizing only one of cyclopentadienyl rings could probably be solved by the use of the ansa compound [Mo(η 5 -C 5 H 4 CH 2 -η 1 -CH 2 )(η 4 -C 5 H 6 )(CO)] [16] that was previously synthesized from [Mo(η 5 -C 5 H 4 CH 2 -η 1 -CH 2 )(CO) 3 ] [17] and cyclopentadiene through a photochemical route. Unfortunately, none of these routes is very practical in the absence of metal vapor synthesis equipment or sound control of the photochemical reactions.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization and Stability of Spirodiene Complexes of Molybdenum(II): New Route to ansa‐Molybdenocene and Ring‐Functionalized Molybdenocene Compounds

2007

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The reactions of [Mo(CO)2(Cp)(NCCH3)2][BF4] (1) with spiro[2.4]hepta‐4,6‐diene and spiro[4.4]nona‐1,3‐diene give the complexes [Mo{η4‐C5H4(CH2)2}(CO)2(Cp)][BF4] (3) and [Mo{η4‐C5H4(CH2)4}(CO)2(Cp)][BF4] (4), respectively. [Mo{η4‐C5H4(CH2)2}(CO)2(Cp)][BF4] (3) is stable towards ring opening at room temperature, but its formation is accompanied by small amounts of ring‐opening products [Mo(η5‐C5H4CH2‐η1‐CH2)(CO)(Cp)][BF4] (5) and [Mo{η5‐C5H4(CH2)2‐η1‐CO}(CO)(Cp)][BF4] (6). With 1,1‐dimethyl‐spiro[2.4]hepta‐4,6‐diene, two isomers with the formula [Mo{η4‐C5H4CH2C(CH3)2}(CO)2(Cp)][BF4] are formed (7 and 8). While the endo‐isomer 7 is stable towards ring opening, the exo‐isomer 8 slowly rearranges to the ring‐opened product [Mo{η5‐C5H4C(CH3)2CH2‐η1‐CO}(CO)(Cp)][BF4] (9). The reaction of [Mo(CO)2(Ind)(NCCH3)2][BF4] (2) with spiro[4.4]nona‐1,3‐diene also gives the diene coordinated species [Mo{η4‐C5H4(CH2)4}(CO)2(Ind)][BF4] (11), which is the first example of a structurally characterized, coordinated, unsubstituted spirodiene. In contrast, reaction of 2 with spiro[2.4]hepta‐4,6‐diene leads directly to the ansa‐cyclopentadienyl complex [Mo(η5‐C5H4CH2‐η1‐CH2)(CO)(Ind)][BF4] (12). Reaction of 12 with bromine or iodine leads to the formation of Cp‐substituted molybdenocene derivatives [Mo{η5‐C5H4(CH2)2X}(CO)(Ind)X][BF4] (13: X = Br, 14: X = I). The compounds [Mo(η5‐C5H4CH2‐η1‐CH2)(CO)(Ind)][BF4] (12) and [MoBr{η5‐C5H4(CH2)2Br}(CO)(Ind)][Br]·0.5H2O (13a) were structurally characterized, and they open the way to new functionalized molybdenocene complexes that have biological applications.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Photochemisches verhalten von tricarbonyl-η5:1-(2-cyclopentadiendiyl)ethyl-molybdän und -wolfram gegenüber cyclischen dienen

Cited by 7 publications

References 13 publications

Reaction of Spiro[2.4]hepta-4,6-diene with Molybdenum(II) Indenyl Compounds: Effects of Substitution in the Indenyl Ligand

Reaction of Spiro[2.4]hepta-4,6-diene with Molybdenum(II) Indenyl Compounds: Effects of Substitution in the Indenyl Ligand

Syntheses, X-ray Crystal Structures, and Solution Behavior of Cationic, Two-Coordinate Gold(I) η²-Diene Complexes

Synthesis, Characterization and Stability of Spirodiene Complexes of Molybdenum(II): New Route to ansa‐Molybdenocene and Ring‐Functionalized Molybdenocene Compounds

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Photochemisches verhalten von tricarbonyl-η5:1-(2-cyclopentadiendiyl)ethyl-molybdän und -wolfram gegenüber cyclischen dienen

Cited by 7 publications

References 13 publications

Reaction of Spiro[2.4]hepta-4,6-diene with Molybdenum(II) Indenyl Compounds: Effects of Substitution in the Indenyl Ligand

Reaction of Spiro[2.4]hepta-4,6-diene with Molybdenum(II) Indenyl Compounds: Effects of Substitution in the Indenyl Ligand

Syntheses, X-ray Crystal Structures, and Solution Behavior of Cationic, Two-Coordinate Gold(I) η2-Diene Complexes

Synthesis, Characterization and Stability of Spirodiene Complexes of Molybdenum(II): New Route to ansa‐Molybdenocene and Ring‐Functionalized Molybdenocene Compounds

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Syntheses, X-ray Crystal Structures, and Solution Behavior of Cationic, Two-Coordinate Gold(I) η²-Diene Complexes