A5038764696- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Organometallic Complex Synthesis and Catalysis
- Catalytic Cross-Coupling Reactions
- Asymmetric Hydrogenation and Catalysis
- Metal complexes synthesis and properties
- Historical Studies in Latin America
- Latin American history and culture
- Crystallography and molecular interactions
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Mexican Socioeconomic and Environmental Dynamics
- Archaeology and Natural History
- Synthetic Organic Chemistry Methods
- Coordination Chemistry and Organometallics
- Catalytic C–H Functionalization Methods
- History and Politics in Latin America
- Carbon dioxide utilization in catalysis
- Catalytic Alkyne Reactions
- Organoboron and organosilicon chemistry
- Magnetism in coordination complexes
- Ferrocene Chemistry and Applications
- Chemical Synthesis and Analysis
- Synthesis and characterization of novel inorganic/organometallic compounds
- Synthesis and Reactions of Organic Compounds
- Historical and socio-economic studies of Spain and related regions
Universidad de Oviedo
2006-2021
National Legal Medicine Institute
2015
Universidad Nacional Autónoma de México
1986-2011
Universidad de Valladolid
2004-2007
Centro de Estudios Monetarios y Financieros
2005
Utrecht University
1998-2000
Chemnitz University of Technology
2000
Centre National de la Recherche Scientifique
1996
Laboratoire de Chimie de Coordination
1996
Université de Rennes
1996
The first trinuclear clusters containing NHC ligands are described; the compound [Ru3(Me2Im)(CO)11](Me2Im=1,3-dimethylimidazol-2-ylidene) is easily converted into [Ru3(mu-H)2(mu3-MeImCH)(CO)9] by a process involving activation of two C-H bonds methyl group that an example degradation metal-coordinated ligand under mild conditions.
Multiple choices: The carbyne C atom of 1 and the carbide 2 arise from an N-methyl group 1,3-dimethylimidazol-2-ylidene. synthesis complex 1, which involves activation three CH bonds group, that 2, requires additional CN bond, provide new examples metal-mediated degradation N-heterocyclic carbenes.
The potentially tridentate coordinating ligands NN′N (2,6-bis[(dimethylamino)methyl]pyridine) and PNP (2,6bis[(diphenylphosphino)methyl]pyridine) react with [RuCl 2 (PPh 3 ) ] to give [mer,trans-RuCl (NN′N)(PPh )] ( 1) (PNP)(PPh (2), respectively.Complex 1 functions as a starting material for variety of Ru[NN′N] complexes.It reacts either or equiv AgOTf (OTf -) SO CF yield monocationic [RuCl(NN′N)(PPh )]OTf (3) [RuOTf(NN′N)(PPh (4), respectively.The molecular structure 4 shows...
Cationic palladium(II) complexes containing the chiral N-heterocyclic carbene (NHC) ligand 1-ethylenethiolate-3-methyl-4-(R)-phenylimidazoline-2-ylidene have been prepared in one-pot reactions that involve oxidative addition of C−S bond methyl levamisolium to [Pd(dba)2] (dba = dibenzylidene acetone). These represent an easy entry into having NHC ligands.
The room-temperature reactions of [Ru3(CO)12] and [Os3(CO)12] with a variety N-heterocyclic carbenes (NHCs) have been studied. reacts easily N,N′-dimethylimidazol-2-ylidene (Me2Im), more slowly N-methyloxazol-2-ylidene (MeOx), very N,N′-dimesitylimidazol-2-ylidene (Mes2Im) to give the corresponding CO substitution products [Ru3(NHC)(CO)11], but it does not react bulky N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (Dipph2Im). DFT calculations shown that [Ru3(Dipph2Im)(CO)11] is minimum in...
Pyrid-2-ylidenes are trapped in solution by [Ru3(CO)12] after being formed deprotonation of N-substituted pyridinium cations. The great basicity these NHC ligands and the polynuclear character ruthenium cluster trigger room temperature orthometalation initial κ1-C2-pyrid-2-ylidene ligands, leading to unprecedented face-capping κ2-C2,C3-pyrid-3-yl-2-ylidene ligands.
The trinuclear complexes [M3(mu-Cl)(mu-S approximately CH)(CO)9] (M=Ru, Os; S CH=1-ethylenethiolate-3-H-4-(S)-phenylimidazolin-2-ylidene) and [M3(mu-H)(mu-S CMe)(CO)9] CMe=1-ethylenethiolate-3-methyl-4-(S)-phenylimidazolin-2-ylidene) have been prepared by treating [Ru3(CO)12] [Os3(CO)10(MeCN)2] with levamisolium chloride or [M3(mu-H)(CO)11]- methyl triflate, respectively. chiral N-heterocyclic carbene-thiolate ligands CH CMe arise from the oxidative addition of C-S bond cations to anionic clusters.
Activation of one CC and three CH bonds associated with a methyl group attached to an organic fragment has been achieved. Two compounds, which arise from the activation two (1) 6,6′-dimethyl-2,2′-bipyridine (Me2bipy), pentanuclear cluster 2, contains carbide ligand arising Me2bipy, were isolated reactions [Ru3(CO)12] Me2bipy. •=CO. Supporting information for this article is available on WWW under http://www.wiley-vch.de/contents/jc_2002/2004/z54066_s.pdf or author. Please note: The...
The thermolysis of the NHC triosmium cluster [Os3(Me2Im)(CO)11] (1a; Me2Im = 1,3-dimethylimidazol-2-ylidene) in toluene at reflux temperature sequentially affords edge-bridged [Os3(µ-H)(µ-κ2-MeImCH2)(CO)10] (2a) and face-capped derivative [Os3(µ-H)2(µ3-κ2-MeImCH)(CO)9] (3a). These products result from sequential oxidative addition one two (3a) N–methyl C–H bonds original ligand. related triruthenium [Ru3(µ-H)2(µ3-κ2-MeImCH)(CO)9] (3b) has been prepared by heating [Ru3(Me2Im)(CO)11] (1b) THF...
Alkoxo complexes [Re(OR)(CO)(3)(N-N)] (R=Me, Et, tBu; N-N=2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'bipyridine (bipy'), 1,10-phenanthroline (phen)) and [M(OMe)(eta(3)-allyl)(CO)(2)(phen)] (M=Mo, W) have been synthesized in good yields using mild conditions by the reaction of sodium alkoxides with [Re(OTf)(CO)(3)(N-N)] [MCl(eta(3)-allyl)(CO)(2)(phen)] precursors. These characterized IR NMR spectroscopy as well X-ray diffraction for [W(OMe)(eta(3)-allyl)(CO)(2)(phen)] (10). The reactions...
Abstract The hydroxo compounds [Re(OH)(CO) 3 (NN)] (NN=bipy, 2 a ; Me bipy, b ) were prepared in biphasic H O/CH Cl medium by reaction of [Re(OTf)(CO) with KOH. In contrast, when anhydrous CH was used, the binuclear hydroxo‐bridged compound [{Re(CO) (bipy)} (μ‐OH)]OTf ( ‐OTf) obtained. Compound (Me bipy)] reacted phenyl acetate or vinyl to afford [Re(OAc)(CO) 4 and phenol acetaldehyde, respectively. reactions [Mo(OH)(η ‐C Me‐2)(CO) (phen)] 1 ), , toward several unsaturated organic...
The cationic cluster complexes [Ru3(CO)10(mu-H)(mu-kappa2N,C-L1Me)]+ (3+; HL1=quinoxaline) and [Ru3(CO)10(mu-H)(mu-kappa2N,C-L2Me)]+ (5+; HL2=pyrazine) have been prepared as triflate salts by treatment of their neutral precursors [Ru3(CO)10(mu-H)(mu-kappa2N,C-Ln)] with methyl triflate. character heterocyclic ligands is responsible for enhanced tendency to react anionic nucleophiles relative that hydrido triruthenium carbonyl clusters N-heterocyclic ligands. These instantaneously lithium...
The reaction of [Ru3(CO)12] with pyrimidine (Hpym) leads to the isomeric cyclometalated derivatives [Ru3(μ-H)(μ-κ2N1,C6-pym)(CO)10] (1) and [Ru3(μ-H)(μ-κ2N1,C2-pym)(CO)10] (2), which have been treated [Me3O][BF4] give corresponding N-methylpyrimidinium [Ru3(μ-H)(μ-κ2N1,C6-pymMe)(CO)10][BF4] (3[BF4]) [Ru3(μ-H)(μ-κ2N1,C2-pymMe)(CO)10][BF4] (4[BF4]). 4[BF4] K-Selectride renders a separable mixture two neutral trinuclear products, [Ru3(μ-H){μ-κ2N1,C2-(6-HpymMe)}(CO)9] (5)...
The tetraruthenium tetrahydrido cluster compound [Ru4(μ-H)4(CO)12] (1) reacts at room temperature with N-heterocyclic carbenes of the 1,3-disubstituted imidazolin-2-ylidene type (R1R2Im) to give carbonyl substitution products [Ru4(μ-H)4(CO)11(R1R2Im)] (R1R2Im = 1,3-dimethylimidazolin-2-ylidene, 2; 1-phenyl-3-methylimidazolin-2-ylidene, 3; 1,3-diphenylimidazolin-2-ylidene, 4; and 1,3-dimesitylimidazolin-2-ylidene, 5). In solution, compounds 2−5 are fluxional in NMR time scale display same...
Six-membered-ring N-heterocyclic carbenes having only one N atom (NHC1N-R6 carbenes) can be easily prepared by simple deprotonation of readily available N-methylpyridinium-type cations with K[N(SiMe3)2]. They have been trapped in solution [Ru3(CO)12] to give novel triruthenium clusters that contain orthometalated NHC1N-R6 carbene ligands a face-capping coordination mode. Four NHC1N-R6-derived compounds general formula [Ru3(μ-H)(μ3-κ2C2,C3-L)(CO)9] (L = N-methylpyrid-3-yl-2-ylidene (1; from...
A series of related platinum σ-acetylide complexes {Pt}C⋮CR ({Pt} = [Pt(C6H3{Me2NCH2}2-2,6)]+) were prepared by reacting lithium acetylides with {Pt}Cl (1) in order to investigate the stability Pt−acetylide σ-bond and their possible application assembly multimetallic compounds containing {Pt} "pincer" unit. This may be achieved η2-coordination acetylide or incorporating a second ligating site anion. Both these approaches are demonstrated herein. {Pt}C⋮CSiMe3 (2) was reacted [M][BF4] ([M]...
The triruthenium dihydrido cluster compound [Ru3(μ-H)2(μ3-κ2-MeImCH)(CO)9] (1), which contains a basic face-capping N-heterocyclic carbene ligand (MeImCH) derived from the activation of two C−H bonds 1,3-dimethylimidazol-2-ylidene (Me2Im), reacts (a) with [HOEt2][BF4] to give cationic trihydrido cluster; (b) HSnPh3 and HSnBu3 tin-containing clusters that arise Sn−H oxidative addition or three molecules tertiary stannane contain an Me2Im is formed by coupling CH fragment MeImCH 1 hydrido...
The reaction of [Ru3(CO)12] with the lithium salt benzophenone imine (LiNCPh2) followed by protonation trifluoroacetic acid leads to η1-1-azavinylidene cluster complex [Ru3(μ-H)(μ-NCPh2)(CO)10] (1). Compound 1 cannot be prepared direct under thermal conditions. Carbonyl substitution and thermolysis reactions on compound some its derivatives are described. Complex reacts 2 equiv bis(diphenylphosphino)methane (dppm) at room temperature give substituted [Ru3(μ-H)(μ-NCPh2)(μ-dppm)(CO)8] (2)...
The binuclear Ru(II) μ2-dinitrogen complex [{RuCl2(η3-NN'N)}2(μ-N2)] (1, NN'N = 2,6-bis[(dimethylamino)methyl]pyridine) is an excellent starting material for the synthesis of mononuclear η2-alkene complexes: mer,trans-[RuCl2(η3-NN'N)(η2-H2CCHR)] (R H, CHCH2, Ph, CH2Ph, CH2Br, CH2OH, CHO, C⋮N, CO2Me; yields 73−93%). These new compounds are stable at room temperature even when alkene carbon atoms substituted with potentially reactive functional groups. Of particular note reaction 1 allyl...
The cationic cluster complexes [Ru(3)(mu-H)(mu-kappa(2)N,C-L(1) Me)(CO)(10)](+) (1(+); HL(1) Me=N-methylpyrazinium), [Ru(3)(mu-H)(mu-kappa(2)N,C-L(2) (2(+); HL(2) Me=N-methylquinoxalinium), and [Ru(3)(mu-H)(mu-kappa(2)-N,C-L(3) (3(+); HL(3) Me=N-methyl-1,5-naphthyridinium), which contain N-heterocyclic ligands, undergo one-electron reduction processes to become short lived, ligand-centered, trinuclear, radical species (1-3) that end in the formation of an intermolecular C--C bond between...
The thermal activation of a triphenylphosphine P−C bond the 48-electron cationic cluster complex [Ru3(μ3-ampy)(PPh3)2(CO)8][BF4] (2; Hampy = 2-amino-6-methylpyridine) leads to phenyl derivative [Ru3(μ-Ph)(μ3-ampy)(μ-PPh2)(PPh3)(CO)7][BF4] (3). Treatment 3 with carbon monoxide regenerates 2 via 50-electron intermediate [Ru3(μ-Ph)(μ3-ampy)(μ-PPh2)(PPh3)(CO)8][BF4]. These reactions represent first reversible reaction reported in carbonyl chemistry. neutral acyl...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTricyclohexylphosphine- versus Triphenylphosphine-Substituted Derivatives of a Face-Bridged Triruthenium Carbonyl Cluster Complex. A Comparative Study Their Synthesis, Structure, and Catalytic Activity in the Homogeneous Hydrogenation DiphenylacetyleneSilvia Alvarez, Pierrette Briard, Javier A. Cabeza, Ignacio del Rio, Jose M. Fernandez-Colinas, Faizel Mulla, Lahcene Ouahab, Victor RieraCite this: Organometallics 1994, 13, 11, 4360–4366Publication...
The synthesis of the first trinuclear carbonyl clusters containing ligands derived from di(2-pyridyl)amine (Hdpa) has been achieved. Treatment [Ru3(CO)12] or [Ru3(CO)10(MeCN)2] with gives cluster complex [Ru3(μ-Η)(μ-η3-dpa-C,N,N)(CO)9] (1). dpa ligand in this compound chelates a Ru atom through both pyridinic nitrogens while attached to another C metalated pyridine ring, keeping amino NH fragment uncoordinated. Curiously, osmium compounds [Os3(μ-Η)(μ-η2-dpa-N,N)(CO)10] (2) and...
The treatment of [Ru3(CO)12] with 6,6'-dimethyl-2,2'-bipyridine (Me2bipy) or 2,9-dimethyl-1,10-phenanthroline (Me2phen) in THF at reflux temperature gives the trinuclear dihydride complexes [Ru3(mu-H)2(mu3-L1)(CO)8] (L1 = HCbipyMe 1 a, HCphenMe b), which result from activation two C-H bonds a methyl group. hexa-, hepta-, and pentanuclear derivatives [Ru6(mu3-H)(mu5-L2)(mu-CO)3(CO)13] (L2 CbipyMe 2 CphenMe [Ru7(mu3-H)(mu5-L2)(mu-CO)2(CO)16] 3 [Ru5(mu-H)(mu5-C)(mu-L3)(CO)13] (L3 bipyMe 4...