PUMA publications for /user/galaktoze/kineticshttps://puma.ub.uni-stuttgart.de/user/galaktoze/kineticsPUMA RSS feed for /user/galaktoze/kinetics2024-03-28T14:21:51+01:00New Ruthenium Nitrosyl Complexes with Tris(1-pyrazolyl)methane (tpm) and 2,2'-Bipyridine (bpy) Coligands. Structure, Spectroscopy, and Electrophilic and Nucleophilic Reactivities of Bound Nitrosylhttps://puma.ub.uni-stuttgart.de/bibtex/21dec763314338889cee5ebfe6faaab5b/galaktozegalaktoze2018-08-09T10:59:25+02:00complex complex;electrochem complex;geometry complex;kinetics complex;oxidn complex;ruthenium crystal hydroxide kinetics nitrosyl optimized prepn pyrazolylmethane reaction redn ruthenium structure <span data-person-type="author" class="authorEditorList "><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Mariela Videla" itemprop="url" href="/person/1a2982ab55012f32a169ef3a1aa9a87c4/author/0"><span itemprop="name">M. Videla</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Julian S. Jacinto" itemprop="url" href="/person/1a2982ab55012f32a169ef3a1aa9a87c4/author/1"><span itemprop="name">J. Jacinto</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Ricardo Baggio" itemprop="url" href="/person/1a2982ab55012f32a169ef3a1aa9a87c4/author/2"><span itemprop="name">R. Baggio</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Maria T. Garland" itemprop="url" href="/person/1a2982ab55012f32a169ef3a1aa9a87c4/author/3"><span itemprop="name">M. Garland</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Priti Singh" itemprop="url" href="/person/1a2982ab55012f32a169ef3a1aa9a87c4/author/4"><span itemprop="name">P. Singh</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Wolfgang Kaim" itemprop="url" href="/person/1a2982ab55012f32a169ef3a1aa9a87c4/author/5"><span itemprop="name">W. Kaim</span></a></span>, </span><span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Leonardo D. Slep" itemprop="url" href="/person/1a2982ab55012f32a169ef3a1aa9a87c4/author/6"><span itemprop="name">L. Slep</span></a></span>, </span> and <span><span itemtype="http://schema.org/Person" itemscope="itemscope" itemprop="author"><a title="Jose A. Olabe" itemprop="url" href="/person/1a2982ab55012f32a169ef3a1aa9a87c4/author/7"><span itemprop="name">J. Olabe</span></a></span></span>. </span><span class="additional-entrytype-information"><span itemtype="http://schema.org/PublicationIssue" itemscope="itemscope" itemprop="isPartOf"><em><span itemprop="journal">Inorganic Chemistry</span>, </em> <em><span itemtype="http://schema.org/PublicationVolume" itemscope="itemscope" itemprop="isPartOf"><span itemprop="volumeNumber">45 </span></span>(<span itemprop="issueNumber">21</span>):
<span itemprop="pagination">8608--8617</span></em> </span>(<em><span>2006<meta content="2006" itemprop="datePublished"/></span></em>)</span>Thu Aug 09 10:59:25 CEST 2018Inorganic Chemistry218608--8617New Ruthenium Nitrosyl Complexes with Tris(1-pyrazolyl)methane (tpm) and 2,2'-Bipyridine (bpy) Coligands. Structure, Spectroscopy, and Electrophilic and Nucleophilic Reactivities of Bound Nitrosyl452006complex complex;electrochem complex;geometry complex;kinetics complex;oxidn complex;ruthenium crystal hydroxide kinetics nitrosyl optimized prepn pyrazolylmethane reaction redn ruthenium structure [Ru(bpy)(tpm)NO](ClO4)3 [tpm = tris(1-pyrazolyl)methane; bpy = 2,2'-bipyridine] was prepd. in a stepwise procedure that involves the conversion of [Ru(bpy)(tpm)Cl]+ into the aqua and nitro intermediates, followed by acidification. The diamagnetic complex crystallizes to exhibit distorted octahedral geometry around the metal, with the Ru-N(O) bond length 1.774(12) {\AA} and the RuNO angle 179.1(12)°, typical for a {RuNO}6 description. The [Ru(bpy)(tpm)NO]3+ ion (I) was characterized by 1H NMR and IR spectroscopies (\textgreek{n}NO = 1959 cm-1) and through d. functional theory calcns. Intense electronic transitions in the 300-350-nm region are assigned through time-dependent (TD)DFT as intraligand \textgreek{p} $\rightarrow$ \textgreek{p}* for bpy and tpm. The d\textgreek{p} $\rightarrow$ \textgreek{p}*(bpy) metal-to-ligand charge-transfer transitions appear at higher energies. Aq. cyclic voltammetric studies show a reversible wave at 0.31 V (vs. Ag/AgCl, 3 M Cl-), which shifts to 0.60 V in MeCN, along with the onset of a wave of an irreversible process at -0.2 V. The waves are assigned to the 1- and two-electron redns. centered at the NO ligand, leading to species with {RuNO}7 and {RuNO}8 configurations, resp. Controlled potential redn. of I in MeCN led to the [Ru(bpy)(tpm)NO]2+ ion (II), revealing a significant downward shift of \textgreek{n}NO to 1660 cm-1 as well as changes in the electronic absorption bands. II was also characterized by ESR, showing an anisotropic signal at 110 K that arises from an S = 1/2 electronic ground state; the g-matrix components and hyperfine coupling tensor resemble the behavior of related {RuNO}7 complexes. Both I and II were characterized through their main reactivity modes, electrophilic and nucleophilic, resp. The addn. of OH- into I generated the nitro complex, with kOH = 3.05 $\times$ 106 M-1 s-1 (25°). This value is among the highest obtained for related nitrosyl complexes and correlates with ENO+/NO, the 1-electron redox potential. Complex II is a robust species toward NO release, although a conversion to I was obsd. in the presence of O2. This reaction afforded a 2nd-order rate law with k = 3.5M-1 s-1 (25°). The stabilization of the NO radical complex is attributed to the high pos. charge of the precursor and to the geometrical and electronic structure as detd. by the neutral tpm ligand. [on SciFinder(R)]