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Cyclopentadienyl/Phenyl Attraction in CpM–L–E–Ph Compounds by CH/π Interactions

18-Mar-2015 | Henri Brunner; Takashi Tsuno, Organometallics, 2015

In the solid state and also in solution CpM–L–E–Ph compounds adopt preferential conformations, in which C–H bonds of the Cp ligand bind to the π system of the phenyl substituent. This holds for CpMo(CO)2–amidinato and −thioamidato as well as for CpM–P(OPh)3 complexes. In the solid state this is ...


Microsolvation, Dimerization, and sp2-Stereoinversion of Monomeric α-(2,6-Diisopropylphenyl)vinyllithium

11-Mar-2015 | Rudolf Knorr; Jakob Ruhdorfer; Petra Böhrer, Organometallics, 2015

The title compound is entirely monomeric in THF as the solvent, but its two ortho-diisopropyl substituents (in contrast to two tert-butyl groups) do not suffice to prevent its dimerization in Et2O: At −107 °C, the disolvated dimer (43% of the total material in monomeric formula units) was ...


Generation of Mono- and Bimetallic Palladium Complexes and Mechanistic Insight into an Operative Metal Ring-Walking Process

04-Mar-2015 | Meital Orbach; Sreejith Shankar; Olena V. Zenkina; Petr Milko; Yael Diskin-Posner; Milko E. van der Boom, Organometallics, 2015

This combined experimental and computational study demonstrates how a metal center can drastically influence the reactivity of a coordinated ligand. We found that the consecutive formation of zerovalent bimetallic complexes proceeds by fast η2-C═C coordination of only one Pd(PEt3)2 moiety, which ...


Structural Diversity in Alkaline Earth Metal Complexes of a Phosphine-Borane-Stabilized 1,3-Dicarbanion

27-Feb-2015 | Keith Izod; Corinne Wills; Salima El-Hamruni; Ross W. Harrington; Paul G. Waddell; Michael R. Probert, Organometallics, 2015

The reaction between (4-tBuC6H4CH2)2Ca and one equivalent of PhP(BH3)(CH2SiMe3)2 (1) in diethyl ether gives the dimeric complex [[PhP(BH3){CH(SiMe3)}2]Ca(OEt2)]2 (2) in good yield. Similar reactions between 1 and one equivalent of either (PhCH2)2Sr(THF) or (PhCH2)2Ba yield the corresponding ...


Aggregation-Induced Emission of Bis(imino)acenaphthene Zinc Complexes: Photophysical Tuning via Methylation of the Flanking Aryl Substituents

19-Feb-2015 | Daniel A. Evans; Lucia Myongwon Lee; Ignacio Vargas-Baca; Alan H. Cowley, Organometallics, 2015

Bis(imino)acenaphthene zinc complexes with methylated aryl substituents have been examined from the standpoint of their photoluminescent properties. Although complexes 1–4 proved to be nonemissive in solution, complexes 1 and 2 were found to emit via an aggregation-induced emission pathway. On ...


Reactions of the Unsaturated Ditungsten Anion [W2Cp2(μ-PCy2)(μ-CO)2]− with C- and P-Based Electrophiles

19-Feb-2015 | M. Angeles Alvarez; M. Esther García; Daniel García-Vivó; Miguel A. Ruiz; M. Fernanda Vega, Organometallics, 2015

The Na+ salt of the title anion reacted with MeI to give a mixture of isomeric methoxycarbyne [W2Cp2(μ-COMe)(μ-PCy2)(μ-CO)] (major) and methyl-bridged [W2Cp2(μ-CH3)(μ-PCy2)(CO)2] (minor) derivatives, following from competitive methylation at the O atoms or at the ditungsten center, respectively. ...


Boryl-Dihydrideborate Osmium Complexes: Preparation, Structure, and Dynamic Behavior in Solution

18-Feb-2015 | Miguel A. Esteruelas; Ana M. López; Malka Mora; Enrique Oñate, Organometallics, 2015

The metal fragment Os(CO)(PiPr3)2 stabilizes boryl-dihydrideborate species, which can be viewed as snapshots of states of B–H oxidative addition of a R2BH molecule and frustrated B–H bond activation of a second one. Complex OsH2(η2-CH2═CHEt)(CO)(PiPr3)2 (2) shows a tendency to dissociate the ...


Coordination Induced Atropisomerism in an NHC-Based Rhodium Macrocycle

18-Feb-2015 | Rhiann E. Andrew; Dominic W. Ferdani; C. André Ohlin; Adrian B. Chaplin, Organometallics, 2015

Reversible interaction with carbon monoxide results in the onset of dynamic atropisomerism at 298 K in an otherwise static NHC-based rhodium pincer complex, [Rh(C^N^C-(CH2)12)(CO)][BArF4] (1, ArF = 3,5-C6H3(CF3)2). The mechanism of this process has been comprehensively interrogated by a ...


Molecular Rods Combining o-Carborane and Bicyclo[1.1.1]pentane Cages: An Insertion of the Triple Bond Located Next to a Highly Strained Cage

17-Feb-2015 | Jiří Kaleta; Zbyněk Janoušek; Marek Nečas; Ctibor Mazal, Organometallics, 2015

Octacarbonyl dicobalt and bis(dimethyl sulfide)decaborane B10H12(Me2S)2 were successfully added to 1,3-diethynylbicyclo[1.1.1]pentane in good yields. This is an interesting example of a cycloaddition reaction achieved next to the bicyclopentane cage that tends to rearrange in many other cases. It ...


Monomer–Dimer Divergent Behavior toward DNA in a Half-Sandwich Ruthenium(II) Aqua Complex. Antiproliferative Biphasic Activity

29-Dec-2014 | Natalia Busto; Marta Martínez-Alonso; José M. Leal; Ana M. Rodríguez; Fernando Domínguez; Ma Isabel Acuña; Gustavo E ..., Organometallics, 2014

The complex [(η6-p-cymene)Ru(OH2)(κ2-N,N-HL1)](OTf)2 (HL1 = 2-pyridin-2-yl-1H-benzimidazole), [2c](OTf)2, undergoes easy deprotonation of the N–H group at physiological pH, producing [(η6-p-cymene)Ru(OH2)(κ2-N,N-L1)]+, [2c′]+, prone to dimerization both in solution and in the solid state. X-ray ...


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