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Russell J Needham, Abraha Habtemariam, Nicolas P E Barry, Guy Clarkson, Peter J Sadler
We report the synthesis of halido Os(II) p-cymene complexes bearing bidentate chelating phenylazobenzothiazole (AZBTZ) ligands. Unlike the analogous phenylazopyridine (AZPY) complexes, AZBTZ-NMe2 is capable of both N,N-coordination to Os(II) and cyclometalation to form N,C-coordinated species. N,C-Coordination occurs via an azo nitrogen and an ortho carbon on the aniline ring, as identified by 1H NMR and X-ray crystallography of [Os(p-cym)(N,N-AZBTZ-NMe2)Cl]PF6 (1a), [Os(p-cym)(N,N-AZBTZ-NMe2)Br]PF6 (2a), [Os(p-cym)(N,C-AZBTZ-NMe2)Br] (2b), and [Os(p-cym)(N,C-AZBTZ-NMe2)I] (3b)...
November 27, 2017: Organometallics
Samantha Lau, Bryan Ward, Xueer Zhou, Andrew J P White, Ian J Casely, Stuart A Macgregor, Mark R Crimmin
The isolable ruthenium(II) bis(dinitrogen) complex [Ru(H)2(N2)2(PCy3)2] (1) reacts with aryl ethers (Ar-OR, R = Me and Ar) containing a ketone directing group to effect sp(2)C-O bond activation at temperatures below 40 °C. DFT studies support a low-energy Ru(II)/Ru(IV) pathway for C-O bond activation: oxidative addition of the C-O bond to Ru(II) occurs in an asynchronous manner with Ru-C bond formation preceding C-O bond breaking. Alternative pathways based on a Ru(0)/Ru(II) couple are competitive but less accessible due to the high energy of the Ru(0) precursors...
September 25, 2017: Organometallics
Xin Yu, Chen-Ho Tung, Wenguang Wang, Mioy T Huynh, Danielle L Gray, Sharon Hammes-Schiffer, Thomas B Rauchfuss
This study describes the structural, spectroscopic, and electrochemical properties of electronically unsymmetrical diiron hydrides. The terminal hydride Cp*Fe(pdt)Fe(dppe)(CO)H ([1(t-H)](0), Cp*(-) = Me5C5(-), pdt(2-) = CH2(CH2S(-))2, dppe = Ph2PC2H4PPh2) was prepared by hydride reduction of [Cp*Fe(pdt)Fe(dppe)(CO)(NCMe)](+). As established by X-ray crystallography, [1(t-H)](0) features a terminal hydride ligand. Unlike previous examples of terminal diiron hydrides, [1(t-H)](0) does not isomerize to the bridging hydride [1(μ-H)](0)...
June 12, 2017: Organometallics
Noémie Lalaoui, Toby Woods, Thomas B Rauchfuss, Giuseppe Zampella
The azadithiolate complex Fe2[(SCH2)26NMe](CO)6 reacts with borane to give an initial 1:1 adduct, which spontaneously decarbonylates to give Fe2[(SCH2)2NMeBH3](CO)5. Featuring a Fe-H-B three-center, two-electron interaction, the pentacarbonyl complex is a structural model for H2 complexes invoked in the [FeFe]-hydrogenases. The pentacarbonyl compound is a "σ complex", where a B-H σ bond serves as a ligand for iron. The structure of this σ complex was characterized by variable-temperature NMR spectroscopy and X-ray crystallography...
June 12, 2017: Organometallics
Eric M Lewandowski, Łukasz Szczupak, Stephanie Wong, Joanna Skiba, Adam Guśpiel, Jolanta Solecka, Valerije Vrček, Konrad Kowalski, Yu Chen
A series of six novel metallocenyl-7-ADCA (metallocenyl = ferrocenyl or ruthenocenyl; 7-ADCA = 7-aminodesacetoxycephalosporanic acid) conjugates were synthesized and their antibacterial properties evaluated by biochemical and microbiological assays. The ruthenocene derivatives showed a higher level of inhibition of DD-carboxypeptidase 64-575, a Penicillin Binding Protein (PBP), than the ferrocene derivatives and the reference compound penicillin G. Protein X-ray crystallographic analysis revealed a covalent acyl-enzyme complex of a ruthenocenyl compound with CTX-M β-lactamase E166A mutant, corresponding to a similar complex with PBPs responsible for the bactericidal activities of these compounds...
May 8, 2017: Organometallics
Xin Yi See, Evan P Beaumier, Zachary W Davis-Gilbert, Peter L Dunn, Jacob A Larsen, Adam J Pearce, T Alex Wheeler, Ian A Tonks
Low-valent Ti(II) species have typically been synthesized by the reaction of Ti(IV) halides with strong metal reductants. Herein we report that Ti(II) species can be generated simply by reacting Ti(IV) imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating Ti(II). In order to probe the generality of this process, Ti(II)-catalyzed alkyne trimerization reactions were carried out with a diverse range of Ti(IV) precatalysts.
April 10, 2017: Organometallics
Mohammad Aghazadeh Meshgi, Rainer Zitz, Małgorzata Walewska, Judith Baumgartner, Christoph Marschner
Most known silatrane chemistry is concerned with examples where the attached silatrane substituent atom is that of an element more electronegative than silicon. The current study features silylated silatranes with a range of electropositive elements attached to the silyl group. The resulting compounds show different degrees of electron density on the silatrane-substituted silicon atom. This directly affects the Si-N interaction of the silatrane which can be monitored either by (29)Si NMR spectroscopy or directly by single crystal XRD analysis of the Si-N distance...
April 10, 2017: Organometallics
Isabelle Chambrier, Dragoş-Adrian Roşca, Julio Fernandez-Cestau, David L Hughes, Peter H M Budzelaar, Manfred Bochmann
The gold(III) methoxide complex (C(∧)N(∧)C)AuOMe (1) reacts with tris(p-tolyl)phosphine in benzene at room temperature under O abstraction to give the methylgold product (C(∧)N(∧)C)AuMe (2) together with O=P(p-tol)3 ((C(∧)N(∧)C) = [2,6-(C6H3(t) Bu-4)2pyridine](2-)). Calculations show that this reaction is energetically favorable (ΔG = -32.3 kcal mol(-1)). The side products in this reaction, the Au(II) complex [Au(C(∧)N(∧)C)]2 (3) and the phosphorane (p-tol)3P(OMe)2, suggest that at least two reaction pathways may operate, including one involving (C(∧)N(∧)C)Au(•) radicals...
April 10, 2017: Organometallics
Mark K Rong, Koen van Duin, Tom van Dijk, Jeroen J M de Pater, Berth-Jan Deelman, Martin Nieger, A W Ehlers, J Chris Slootweg, Koop Lammertsma
Highly stable iminophosphanes, obtained from alkylating nitriles and reaction of the resulting nitrilium ions with secondary phosphanes, were explored as tunable P-monodentate and 1,3-P,N bidentate ligands in rhodium complexes. X-ray crystal structures are reported for both κ(1) and κ(2) complexes with the counterion in one of them being an unusual anionic coordination polymer of silver triflate. The iminophosphane-based ruthenium(II)-catalyzed hydration of benzonitrile in 1,2-dimethoxyethane (180 °C, 3 h) and water (100 °C, 24 h) and under solvent free conditions (180 °C, 3 h) results in all cases in the selective formation of benzamide with yields of up to 96%, thereby outperforming by far the reactions in which the common 2-pyridyldiphenylphosphane is used as the 1,3-P,N ligand...
March 13, 2017: Organometallics
Matthew C Leclerc, Bulat M Gabidullin, Jason G Da Gama, Stephanie L Daifuku, Theresa E Iannuzzi, Michael L Neidig, R Tom Baker
Herein, a recently reported polyfluoroalkenyl imidazolium salt is shown to react with nitrogen-, oxygen- and sulfur-based nucleophiles at the C β position in a stereoselective and regioselective fashion, without the use of a transition metal. In contrast, reactivity with 1-methylimidazole demonstrates net substitution at C α . This product reacts quantitatively with water, affording clean transformation of a difluoromethylene group to give an α,β-unsaturated trifluoromethyl ketone. Further reactivity studies demonstrate that the difluoromethyl fragment of an N-heterocyclic fluoroalkene is capable of direct C-C bond formation with NaCp through loss of sodium fluoride and double C-F bond activation (Cp = cyclopentadienide)...
February 27, 2017: Organometallics
Mohammad Aghazadeh Meshgi, Judith Baumgartner, Viatcheslav V Jouikov, Christoph Marschner
Several silatranyl -substituted oligosilanes were prepared starting from bis(trimethylsilyl)silatranylsilanide. Electrochemical and theoretical investigations of some oligosilanes revealed that electrooxidation occurs by formation of a short-lived cation radical. This species undergoes structural relaxation to form a pair of conformers, with endo and exo relationships with respect to the Si-N interaction. Reaction of a 1,4-disilatranyl-1,4-disilanide with 1,2-dichlorotetramethyldisilane gave a mixture of cis and trans diastereomers of a cyclohexasilane with the trans isomer showing a diminished Si-N distance...
January 23, 2017: Organometallics
Kristine Klimovica, Kristin Kirschbaum, Olafs Daugulis
Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a. The upper limit of ΔG(‡), assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with ΔG298(‡) = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9, with ΔG298(‡) = 16...
September 12, 2016: Organometallics
Małgorzata Walewska, Johann Hlina, Judith Baumgartner, Thomas Müller, Christoph Marschner
In order to estimate the reactivity of disilylated germylene phosphine adducts, a cyclic version of this compound class was reacted with a number of different reagents. Reactions with the chalcogens sulfur, selenium, and tellurium led to dimers of the heavy ketone analogues. Reactions with water and ethyl bromide proceeded to give the respective oxidized germanol and germyl bromide. Two different reactions with alkynes were observed which led either to a germacyclopropene, by addition of tolane to the germylene, or to a silagermacyclobutene, likely formed by addition of the alkyne across a silagermene...
August 22, 2016: Organometallics
Yiu Fung Mui, Jacob Fernández-Gallardo, Benelita T Elie, Ahmed Gubran, Irene Maluenda, Mercedes Sanaú, Oscar Navarro, María Contel
We report on the synthesis, characterization, and stability studies of new titanocene complexes containing a methyl group and a carboxylate ligand (mba = -OC(O)-p-C6H4-S-) bound to gold(I)-N-heterocyclic carbene fragments through the thiolate group: [(η(5)-C5H5)2TiMe(μ-mba)Au(NHC)]. The cytotoxicities of the heterometallic compounds along with those of novel monometallic gold-N-heterocyclic carbene precursors [(NHC)Au(mbaH)] have been evaluated against renal, prostate, colon, and breast cancer cell lines...
May 9, 2016: Organometallics
Andrew J Hoover, Mark Lazari, Hong Ren, Maruthi Kumar Narayanam, Jennifer M Murphy, R Michael van Dam, Jacob M Hooker, Tobias Ritter
Translation of new (18)F-fluorination reactions to produce radiotracers for human positron emission tomography (PET) imaging is rare because the chemistry must have useful scope and the process for (18)F-labeled tracer production must be robust and simple to execute. The application of transition metal mediators has enabled impactful (18)F-fluorination methods, but to date none of these reactions have been applied to produce a human-injectable PET tracer. In this article we present chemistry and process innovations that culminate in the first production from [(18)F]fluoride of human doses of [(18)F]5-fluorouracil, a PET tracer for cancer imaging in humans...
April 11, 2016: Organometallics
Noelia Casanova, Miguel A Esteruelas, Moisés Gulías, Carmen Larramona, José L Mascareñas, Enrique Oñate
The amide-directed synthesis of five-coordinate osmium alkylidene derivatives from alkynes is reported. These types of complexes, which have been elusive until now because of the tendency of osmium to give hydride alkylidyne species, are prepared by reaction of the dihydride OsH2Cl2(P(i)Pr3)2 (1) with terminal alkynes containing a distal amide group. Complex 1 reacts with N-phenylhex-5-ynamide and N-phenylhepta-6-ynamide to give OsCl2{=C(CH3)(CH2) n NH(CO)Ph}(P(i)Pr3)2 (n = 3 (2), 4 (3)). The relative position of carbonyl and NH groups in the organic substrates has no influence on the reaction...
January 25, 2016: Organometallics
Daniel L Crossley, Jessica Cid, Liam D Curless, Michael L Turner, Michael J Ingleson
The addition of AlCl3 to four-coordinate boranes of the general formula (C-N-chelate)BCl2 results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl](+). The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl3 were sufficient to effect high-yielding arylation of (C-N-chelate)BCl2. Boro-destannylation is more rapid than boro-desilylation and leads to double arylation at the boron center, whereas in reactions with arylsilanes either single or double arylation occurs dependent on the nucleophilicity of the arylsilane and on the electrophilicity of the borenium cation...
December 28, 2015: Organometallics
Alexander F R Kilpatrick, Jennifer C Green, F Geoffrey N Cloke
Bonding in the bis(pentalene)dititanium "double-sandwich" species Ti2Pn2 (Pn = C8H6) and its interaction with other fragments have been investigated by density functional calculations and fragment analysis. Ti2Pn2 with C 2v symmetry has two metal-metal bonds and a low-lying metal-based empty orbital, all three frontier orbitals having a1 symmetry. The latter may be regarded as being derived by symmetric combinations of the classic three frontier orbitals of two bent bis(cyclopentadienyl) metal fragments. Electrochemical studies on Ti2Pn(†) 2 (Pn(†) = 1,4-{Si(i)Pr3}2C8H4) revealed a one-electron oxidation, and the formally mixed-valence Ti(II)-Ti(III) cationic complex [Ti2Pn(†) 2][B(C6F5)4] has been structurally characterized...
October 26, 2015: Organometallics
Alexander F R Kilpatrick, Jennifer C Green, F Geoffrey N Cloke
The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti2Pn(†) 2 (1) (Pn(†) = 1,4-{Si(i)Pr3}2C8H4) with CO2 is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO2 reaction is performed at -78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO2 molecule bound symmetrically to the two Ti centers in a μ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO2 is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3...
October 26, 2015: Organometallics
Behnaz Ghaffari, Britt A Vanchura, Ghayoor A Chotana, Richard J Staples, Daniel Holmes, Robert E Maleczka, Milton R Smith
Catalytic C-H borylation using the five-coordinate tris-boryl complex (dippe)Ir(Bpin)3 (5a, dippe = 1,2-bis(diisopropylphosphino)ethane) has been examined using (31)P{(1)H} and (1)H NMR spectroscopy. Compound 5a was shown to react rapidly and reversibly with HBpin to generate a six-coordinate borylene complex, (dippe)Ir(H)-(Bpin)2(BOCMe2CMe2OBpin) (6), whose structure was confirmed by X-ray crystallography. Under catalytic conditions, the H2 generated from C-H borylation converted compound 6 to a series of intermediates...
October 12, 2015: Organometallics
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