Strain-Induced Cleavage of Carbon−Carbon Bonds: Bridge Rupture Reactions of Group 8 Dicarba[2]metallocenophanes

Herbert, David E.; Gilroy, Joe B.; Staubitz, Anne; Haddow, Mairi F.; Harvey, Jeremy N.; Manners, Ian

doi:10.1021/ja9087049

Cited by 36 publications

(36 citation statements)

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“…Electron correlation effects were considered by using DFT methods that have evolved as a practical and effective computational tool, especially for organometallic compounds [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32]. Thus, two DFT methods were used in this study.…”

Section: Theoretical Methodsmentioning

confidence: 99%

Binuclear dimethylaminoborole iron carbonyls: iron–iron multiple bonding versus nitrogen → iron dative bonding

Chen

Liu

et al. 2012

Theor Chem Acc

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Theoretical studies show that pendant dimethylamino groups can play a significant role in the chemistry of unsaturated binuclear dimethylaminoborole iron carbonyls. For [C 4 H 4 BN(CH 3 ) 2 ] 2 Fe 2 (CO) 5 , the lowest energy structures have single CO bridges and Fe-Fe single bonds of lengths *2.8 Å . The lowest energy [C 4 H 4 BN (CH 3 ) 2 ] 2 Fe 2 (CO) n (n = 4, 3) structures have two bridging CO groups with Fe=Fe double bonds of lengths *2.5 Å for n = 4 and three bridging CO groups with Fe:Fe triple bonds of lengths *2.2 Å for n = 3. These structures are similar to structures previously found for the corresponding methylborole derivatives (C 4 H 4 BCH 3 )Fe 2 (CO) n . However, slightly higher energy [C 4 H 4 BN(CH 3 ) 2 ] 2 Fe 2 (CO) n (n = 4, 3) structures are found in which dimethylaminoborole is a six-electron donor bridging ligand using electron pairs from the nitrogen atom as well as from the two C=C double bonds. For the more highly unsaturated [C 4 H 4 BN (CH 3 ) 2 ] 2 Fe 2 (CO) n (n = 2, 1), low energy singlet (n = 2) and triplet (n = 1) perpendicular structures are also found with similar bridging six-electron donor dimethylaminoborole ligands. In addition, highly unsaturated [C 4 H 4 BN(CH 3 ) 2 ] 2 Fe 2 (CO) n (n = 3, 2, 1) structures are found with agostic hydrogen atoms bridging an iron-carbon bond.Keywords Iron Á Boroles Á Metal carbonyls Á Dimethylaminoborole Á Metal-metal bonding Á Nitrogen-iron dative bonding Á Density functional theory Dedicated to Professor Eluvathingal Jemmis and published as part of the special collection of articles celebrating his 60th birthday. This paper is dedicated to Professor Eluvathingal Jemmis on the occasion of his 60th birthday in recognition of his major contributions to theoretical chemistry, especially those related to boron compounds. Particularly inspiring to us has been Professor Jemmis' work on electron counting as a means to qualitatively understand electronic structures.Electronic supplementary material The online version of this article (

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Section: Theoretical Methodsmentioning

confidence: 99%

Binuclear dimethylaminoborole iron carbonyls: iron–iron multiple bonding versus nitrogen → iron dative bonding

Chen

Liu

et al. 2012

Theor Chem Acc

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“…NaCp) which do not attack at Si [15]. Furthermore, as discussed in the previous section, cleavage of the bridge EeE bond has been demonstrated for a variety of [2]metallocenophanes [1f, 16,17,22], Until recently, the reactivity modes of [n]metallocenophanes were confined to these aforementioned bond-cleavage processes, with the concomitant release of molecular ring-strain. However, in a recent report a new mode of [n]metallocenophane reactivity based on metalemetal bond formation was elucidated.…”

Section: Metalemetal Bond Formation By Strained Ruthenocenophanesmentioning

confidence: 98%

“…In 2010, the results of a detailed investigation into the thermal reactivity of a series of dicarba[2]ferrocenophanes 10 e rac-14 (Schemes 3 and 4) were reported [16]. Rather than undergoing ROP, tetramethyl-substituted 11 afforded ring-opened, vinyl-substituted metallocene 12 under thermolysis conditions (240 C) (Scheme 3).…”

Section: Bridge Cleavage Reactions With Strained [2]ferrocenophanesmentioning

confidence: 99%

Recent developments with strained metallocenophanes

Russell

Musgrave

Stoll

et al. 2015

Journal of Organometallic Chemistry

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“…Computational studies on this system have confirmed the relative thermodynamic preference for the rac isomer over the meso form, a property reflected in the experimentally determined relative C−C bond lengths of the meso (1.612(3) Å) and rac isomers (1.565(7) Å). 84 The differences in observed reactivity for these species were rationalized through the presence or absence of hydrogen at the α position relative to the carbon atoms in the bridge. Thus, in species 35, an α-hydrogen facilitates H • abstraction and radical disproportionation to afford the ferrocene derivative 53.…”

Section: Recent Work On Strained [2]ferrocenophanesmentioning

confidence: 99%

Strained Ferrocenophanes

2013

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The linking of the cyclopentadienyl rings of ferrocene by a short ansa [n] bridge gives rise to a broad class of strained organometallic rings, which incorporate the ferrocenyl fragment and a large number of possible bridging components. The resulting [n]ferrocenophanes exhibit fascinating structures and reactivity, and interesting comparisons can be drawn between these species and the familiar strained cyclic organic molecules. Providing the bridging moiety is sufficiently short as to induce strain, [n]ferrocenophanes have the propensity to undergo ring-opening reactions, in many cases to yield high-molecular-weight polyferrocenes with a range of interesting properties. This review aims to summarize the recent advances in the field, focusing on the preparation, structural characterization, electronic structure, and unusual reactivity of strained ferrocenophanes.

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Strain-Induced Cleavage of Carbon−Carbon Bonds: Bridge Rupture Reactions of Group 8 Dicarba[2]metallocenophanes

Cited by 36 publications

References 83 publications

Binuclear dimethylaminoborole iron carbonyls: iron–iron multiple bonding versus nitrogen → iron dative bonding

Binuclear dimethylaminoborole iron carbonyls: iron–iron multiple bonding versus nitrogen → iron dative bonding

Recent developments with strained metallocenophanes

Strained Ferrocenophanes

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