Cyclobutadienemetal complexes

EFRATY, A.

doi:10.1021/cr60309a003

Cited by 270 publications

(125 citation statements)

References 98 publications

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“…What was done up to 1977 is summarized very thoroughly in the lengthy Chemical Reviews article by Avi Efraty. 91 (See also later reviews in which (cyclobutadiene)iron tricarbonyl complexes are covered. 92 ) However, some of the other chemistry of (cyclobutadiene)iron tricarbonyl is very interesting and worth discussing.…”

Section: After the Breakthrough Synthesis: Rapid Development Of Tmentioning

confidence: 99%

(Cyclobutadiene)iron TricarbonylA Case of Theory before Experiment

Seyferth

2002

Organometallics

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Section: After the Breakthrough Synthesis: Rapid Development Of Tmentioning

confidence: 99%

(Cyclobutadiene)iron TricarbonylA Case of Theory before Experiment

Seyferth

2002

Organometallics

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“…They are included in the review by Efraty on metal cyclobutadiene complexes. 142 The thermally very stable complex (2,2′-bipyridine)(tetramethylcyclobutadiene)nickel 143 does not react with added donor ligands, e.g., bipyridine or triphenylphosphine; however, CO ( 155 (eq 21) could isolate complexes 65, however in low yields.…”

Section: B [2+2] Metal-assisted Cycloaddition Reactionsmentioning

confidence: 99%

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

1997

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“…The strategy of using metals to construct and stabilize reactive p-systems has met with much success, for example, affording otherwise inaccessible organic groups, such as the square, rather than rectangular form of cyclobutadiene 5 . Furthermore, metal p-complexes find numerous applications in organic synthesis and catalysis, where complexation of a metal can increase or invert the reactivity of p-systems [6][7][8] .…”

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confidence: 99%

Reductive assembly of cyclobutadienyl and diphosphacyclobutadienyl rings at uranium

et al. 2013

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Despite the abundance of f-block-cyclopentadienyl, arene, cycloheptatrienyl and cyclooctatetraenide complexes, cyclobutadienyl derivatives are unknown in spite of their prevalence in the d-block. Here we report that reductive [2 þ 2]-cycloaddition reactions of diphenylacetylene and (2,2-dimethylpropylidyne)phosphine with uranium(V)-inverted sandwich 10p-toluene tetra-anion complexes results in the isolation of inverted sandwich cyclobutadienyl and diphosphacyclobutadienyl dianion uranium(IV) complexes. Computational analysis suggests that the bonding is predominantly electrostatic. Although the c 4 molecular orbital in the cyclobutadienyl and diphosphacyclobutadienyl ligands exhibits the correct symmetry for d-bonding to uranium, the dominant covalent contributions arise from p-bonding involving c 2 and c 3 orbital combinations. This contrasts with uranium complexes of larger arenes and cyclo-octatetraenide, where d-bonding dominates. This suggests that the angular requirements for uranium to bond to a small four-membered ring favours p-bonding, utilizing 5f-instead of 6d-orbitals, over d-bonding that is favoured with larger ligands, where 6d-orbitals can become involved in the bonding.

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Cyclobutadienemetal complexes

Cited by 270 publications

References 98 publications

(Cyclobutadiene)iron TricarbonylA Case of Theory before Experiment

(Cyclobutadiene)iron TricarbonylA Case of Theory before Experiment

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

Reductive assembly of cyclobutadienyl and diphosphacyclobutadienyl rings at uranium

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