Source:http://linkedlifedata.com/resource/pubmed/id/15580647
| Subject | Predicate | Object | Context |
|---|---|---|---|
| pubmed-article:15580647 | rdf:type | pubmed:Citation | lld:pubmed |
| pubmed-article:15580647 | lifeskim:mentions | umls-concept:C0006030 | lld:lifeskim |
| pubmed-article:15580647 | lifeskim:mentions | umls-concept:C0302583 | lld:lifeskim |
| pubmed-article:15580647 | lifeskim:mentions | umls-concept:C1704675 | lld:lifeskim |
| pubmed-article:15580647 | pubmed:issue | 2 | lld:pubmed |
| pubmed-article:15580647 | pubmed:dateCreated | 2005-1-10 | lld:pubmed |
| pubmed-article:15580647 | pubmed:abstractText | A comparison of the molecular structures of mono-, di- and tetraborylated ferrocenes [Fc{B(R(1))(R(2))}] (R(1)/R(2)=Br/Br, Br/Fc, Br/Me, Me/Me, Me/OH, OMe/OMe), 1,1'-[fc{B(R(1))(R(2))}(2)] (R(1)/R(2)=Br/Br, Br/Me, OMe/OMe), and 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)] revealed the boryl substituent(s) to be bent out of the Cp ring plane towards the iron center. The corresponding dip angle alpha* decreases with decreasing Lewis acidity of the boron atom and with increasing degree of borylation at the ferrocene core. This trend is well reproduced by DFT calculations (including [FcBH(2)], not yet accessible experimentally). A Bader analysis of the electron density topology of [FcBH(2)] (alpha*=26.5 degrees ; BP86/TZVP) clearly showed that there is no direct iron-boron bonding in this compound. Instead, strongly delocalized orbital interactions have been identified that involve the boron p orbital, C(ipso) of the adjacent Cp ring, d orbitals at iron, and a through-space interaction with the second Cp ring. A second important factor is attractive electrostatic interactions, which are enhanced upon ligand bending. Cyclic voltammetric measurements on the series [FcBMe(2)], 1,1'-[fc(BMe(2))(2)], and 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)] indicate a substantial anodic shift in the oxidation potential of the central iron atom upon introduction of BMe(2) substituents. Addition of 4-dimethylaminopyridine (DMAP) does not just counterbalance this effect, but leads to a cathodic shift of the Fe(II)/Fe(III) redox transition far beyond the half-wave potential of parent ferrocene. In the Mossbauer spectra, a continuous decrease in the quadrupole splitting (QS) is observed upon going from parent ferrocene to [FcBMe(2)], to 1,1'-[fc(BMe(2))(2)], and to 1,1',3,3'-[Fe{C(5)H(3)(BMe(2))(2)}(2)]. In contrast, no significant differences are found between the QS values of ferrocene, [Fc(BMe(2)-DMAP)], and 1,1'-[fc(BMe(2)-DMAP)(2)]. | lld:pubmed |
| pubmed-article:15580647 | pubmed:language | eng | lld:pubmed |
| pubmed-article:15580647 | pubmed:journal | http://linkedlifedata.com/r... | lld:pubmed |
| pubmed-article:15580647 | pubmed:status | PubMed-not-MEDLINE | lld:pubmed |
| pubmed-article:15580647 | pubmed:month | Jan | lld:pubmed |
| pubmed-article:15580647 | pubmed:issn | 0947-6539 | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:BatsJan WJW | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:WagnerMatthia... | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:HerberRolfe... | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:HolthausenMax... | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:BolteMichaelM | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:LeinMatthiasM | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:ScheibitzMatt... | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:NowikIsraelI | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:LernerH-Wolfr... | lld:pubmed |
| pubmed-article:15580647 | pubmed:author | pubmed-author:KrappAndreasA | lld:pubmed |
| pubmed-article:15580647 | pubmed:issnType | lld:pubmed | |
| pubmed-article:15580647 | pubmed:day | 7 | lld:pubmed |
| pubmed-article:15580647 | pubmed:volume | 11 | lld:pubmed |
| pubmed-article:15580647 | pubmed:owner | NLM | lld:pubmed |
| pubmed-article:15580647 | pubmed:authorsComplete | Y | lld:pubmed |
| pubmed-article:15580647 | pubmed:pagination | 584-603 | lld:pubmed |
| pubmed-article:15580647 | pubmed:dateRevised | 2009-8-4 | lld:pubmed |
| pubmed-article:15580647 | pubmed:year | 2005 | lld:pubmed |
| pubmed-article:15580647 | pubmed:articleTitle | C5H4-BR2 bending in ferrocenylboranes: a delocalized through-space interaction between iron and boron. | lld:pubmed |
| pubmed-article:15580647 | pubmed:affiliation | Institut für Anorganische Chemie, J.W. Goethe-Universität Frankfurt, Marie-Curie-Strasse 11, 60439 Frankfurt/Main, Germany. | lld:pubmed |
| pubmed-article:15580647 | pubmed:publicationType | Journal Article | lld:pubmed |