Ring-slippage chemistry of transition metal cyclopentadienyl and indenyl complexes

O’Connor, J. M.; Casey, Charles P.

doi:10.1021/cr00078a002

Cited by 491 publications

(293 citation statements)

References 54 publications

Supporting

Mentioning

279

Contrasting

Unclassified

Order By: Relevance

“…The cyclopentadienyl half sandwich analogues complexes of the composition [(h 5 -indenyl)MLn ]displayanenhanced reactivity in SN1and SN2s ubstitution reactions [5][6][7][8] and several other reactions [9][10][11]. The reason for this reactivityi st he so called ¢ indenyl effect¢ [12].…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of bis(η5-1-tert-butylindenyl)cobalt(II), Co(C13H15)2

Guo¹,

Hauptmann²,

Belaj³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

View full text Add to dashboard Cite

C 26 H 30 Co, monoclinic, P 12 1 / n 1(no. 14), a =9.932(4) Å, b =10.552(4) Å, c =10.646(5) Å, b =113.76(5)°, Source of materialToasolution of t -butylindene (1.88 g, 10.9 mmol) in hexane asolution of n -BuLi(10.9 mmol) in hexane wasadded slowly at0°C under stirring. The resulting white precipitate wasf iltered and washed with hexane. The lithium t -butylindenid wassuspended in THFand Co(acac)2 (1.4 g, 5.5 mmol) wasadded at-78°C.The reaction mixturew ass tirred for 8hat-78°Cand then slowly warmed up to room temperature overnight. The reaction mixture wasfiltered and stored at-30°C.Afterone week the product was obtained asdark red crystals (yield 0.48 g, 11 %). DiscussionSince the first synthesisofferrocene [1] sandwich complexes are atopic of greatinterest and alarge number of half sandwich, sandwich, triple deckerand multi decker complexes were synthesized

show abstract

Section: Discussionmentioning

confidence: 99%

Crystal structure of bis(η5-1-tert-butylindenyl)cobalt(II), Co(C13H15)2

Guo¹,

Hauptmann²,

Belaj³

et al. 2007

Zeitschrift Für Kristallographie - New Crystal Structures

View full text Add to dashboard Cite

show abstract

“…Fewer examples of associative activation have been identified (27)(28)(29)(30). The latter require an ancillary ligand capable of removing an electron pair in order to avoid formation of high-energy 20 e-species.…”

Section: Methodsmentioning

confidence: 99%

“…The latter require an ancillary ligand capable of removing an electron pair in order to avoid formation of high-energy 20 e-species. Established cases involve hapticity decreases (-q5+-q3 "ring slippage" (27)) of indenyl or cyclopentadienyl or linear+bent NO isomerization (31). In a relevant study Landon and Brill (3) reported second-order kinetics for the Arbuzov rearrangement of -q 5 -~p~o ( d p p e )~ with P(OMe)3 and steric inhibition for the increased bite-angle ligand dppp (1,3-bis(dipheny1-phosphino)propane), implying an associative reaction.…”

Section: Methodsmentioning

confidence: 99%

Evidence for an intramolecular transition metal Arbuzov reaction

Chen¹,

Jablonski²,

Bridson³

1996

Can. J. Chem.

View full text Add to dashboard Cite

Reaction of [CpCo(C3F7)(I)(L)], (L = PPh,Me (la), PPhMe, (lb), PMe, (lc), and PPh(OMe), (2)), with PPh(OMe), affords diastereomeric Co-and P-chiral metallophosphinates CpCo(C3F7)(L)(P(0)Ph(OMe)), 4a,b,c and 6, respectively. The solid state structure and relative configuration of the lower Rf diastereomeric phosphinate CpCo(C3F7)(PPh(0Me),)(P(O)Ph(OMe)), 6-2, was determined by X-ray diffraction. RR;SS-6-2 crystallizes in the triclinic system with space group PT(no. 2), with a = 12.928(4) A, b = 14.683(4) A, c = 7.666(2) A, a = 103.50(2)O, p = 101.31(3)", y = 109.50(2)", V = 1272.8(7) A3, Z = 2, and R = 0.036 (R,, = 0.030) for 2867 reflections with I > 3.00a(T). CpCo(C,F,)(I)(PPh(OMe),), 2, reacts with PPh,Me to yield the same Co-and P-chiral phosphinate products as obtained for the reaction of l a with PPh(OMe),, albeit with different optical yields. The product stereochemistry is not accounted for by the established mechanism for transition metal Arbuzov-like dealkylations, which requires formation of a common, ionic intermediate [CpCo(C3F7)(PPh,Me)(PPh(OMe),)]+, 3, via iodide substitution and subsequent nucleophilic attack at carbon. A parallel intramolecular dealkylation pathway is proposed to account for the results.

show abstract

“…Possible mechanism for initial attack of the '*U-ion on a carbonyl ligand and the predicted extent of incorporation of the '*O atom in the ions formed by loss of two and three carbon monoxide molecules, respectively. metal centre could proceed as illustrated in Scheme 2 for the reaction with CpMn(CO)s. In this hypothetical scheme, the reaction at the metal centre is assumed to involve a q5 to q3 change in the bonding of the C5H5 ligand prior to attack at the manganese atom [29], whereas the reaction at the Cp ligand is presumed to occur from the exo-side of the ring as suggested for the comparable reaction of 0' -with the COCOS compound [lo]. The mechanistic proposals in Schemes 1 and 2 lead to the prediction that the '*O atom is retained in the product ions generated by the loss of two carbon monoxide molecules irrespective of the initial site of attack (vide infra).…”

Section: Site Of Attack By the O'-ionmentioning

confidence: 99%

Regioselectivity in the gas-phase reactions of the O− radical anion with (η5-cyclopentadienyl)tricarbonylmanganese(I) and (η5-methylcyclopentadienyl)tricarbonylmanganese(I): formation and structure of C5H5MnO−n and C6H7MnO−n (n = 1, 2) ions

Berg

Ingemann

Nibbering

1994

International Journal of Mass Spectrometry and Ion Processes

View full text Add to dashboard Cite

Regioselectivity in the gas-phase reactions of the O-* radical; anion with (n5-cyclopentadienyl) tricarbonylmanganese(I) and (n5-methylcyclopentadienyl) tricarbonylmanganese(I). Formation and structure of C5H5MnO(n)-and C6H7MnO(n)-(n=1,2)ions. van den Berg, K.J.; Ingemann Jorgensen, S.; Nibbering, N.M.M. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. CH$pMn(CO)3, have been studied with Fourier transform ion cyclotron resonance. The main reactions are (i) proton abstraction, (ii) loss of COz, and (iii) expulsion of two or three CO molecules from the collision complex. Initial attack on a CO ligand is the main process as indicated by experiments with '*O'-and the ion/molecule reactions of the product ions resulting from the loss of three CO molecules with water, aliphatic alcohols, methanethiol and SO,. The attack on a CO ligand followed by loss of three CO molecules is suggested to yield C5H5MnO-ions with a (cyclopentadienone)MnHstructure in the reaction with CpMn(C0)3 and (methylcyclopentadienone)MnHions if CH$pMn(C0)3 is the substrate. A possible mechanism for the process leading to the indicated transformation of the Cp and CH,Cp ligands into C5H40 and CH&H30 ligands, respectively, is discussed together with the formation of (fulvene)Mn(OH)-ions following attack of O'-on CH$pMn(CO),. The (cyclopentadienone)MnHand (methylcyclopentadienone)MnHions react with NzO by oxygen atom abstraction to form C5H5MnO; and C6H7MnO; ions, respectively.

show abstract

Ring-slippage chemistry of transition metal cyclopentadienyl and indenyl complexes

Cited by 491 publications

References 54 publications

Crystal structure of bis(η5-1-tert-butylindenyl)cobalt(II), Co(C13H15)2

Crystal structure of bis(η5-1-tert-butylindenyl)cobalt(II), Co(C13H15)2

Evidence for an intramolecular transition metal Arbuzov reaction

Regioselectivity in the gas-phase reactions of the O− radical anion with (η5-cyclopentadienyl)tricarbonylmanganese(I) and (η5-methylcyclopentadienyl)tricarbonylmanganese(I): formation and structure of C5H5MnO−n and C6H7MnO−n (n = 1, 2) ions

Contact Info

Product

Resources

About