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Antonio F. Antiñolo García
Actividad Actual:
Catedrático de Universidad de Química Inorgánica
Breve resumen del CV
Nacido en Cartagena en
Julio de 1956
Licenciado en Químicas por la Universidad de Murcia en
1974-1978 con la calificación de Sobresaliente
Doctorado por la Universidad de Alcalá 1982 con al
calificación de Sobresaliente “Cum Laude”
Estancia Postdoctoral en la University of Sussex ( Reino
Unido 1983-1984)
Profesor Titular de Universidad del Área de Química Inorgánica
en la Universidad de Alcalá 1985-1990.
Profesor Titular de Universidad del Área de Química
Inorgánica en la Universidad de Castilla La Mancha 1990-1999
Profesor Invitado en la Universidad de la Bourgogne
(Francia 1995)
Catedrático de Universidad de Química Inorgánica en la
Universidad de Castilla La Mancha 1999
Profesor Invitado en la Universidad de la Bourgogne
(Francia 2001)
Decano de la Facultad de Químicas de La Universidad de
Castilla la Mancha(1997-2009).
Actividad Docente
Docencia en Química General, Inorgánica, de la Coordinación
y Organometálica, primer ciclo, segundo ciclo y cursos de doctorado.
Actividad Investigadora
Síntesis, caracterización estructural y estudios de
reactividad química de derivados organometálicos de elementos de los primeros
grupos de transición, titanio, zirconio, niobio y tántalo. Síntesis de
catalizadores para procesos de polimerización de olefinas(metalocenos).
v
Mas de treinta proyectos de investigación subvencionados
v
Cientosesentaicinco publicaciones científicas en revistas de carácter
internacional.
v
Diez conferencias científicas invitadas en congresos
v
Casi
doscientas comunicaciones en congresos nacionales e
internacionales
v
Doce tesis doctorales dirigidas.
v
Trece tesinas de licenciatura.
Publicaciones seleccionadas
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158.-Antonio Antiñolo,
Santiago García-Yuste, Isabel Lopez Solera, Antonio Otero, Juan Carlos
Pérez-Flores, Rebeca Reguillo-Carmona, Elena Villaseñor, Eva Santos, Erik
Zuidema and Carles Bo.
Reactions of alkynes with phosphido niobocenes: a combined experimental and
theoretical study
Dalton Trans., 2010, 39, 1962–1971
159.-Carlos Alonso-Moreno,
Fernando Carrillo-Hermosilla, Andres Garces, Antonio Otero, Isabel Lopez-Solera,
Ana M. Rodríguez,and Antonio Antiñolo.
Simple,
Versatile, and Efficient Catalysts for Guanylation of Amines
Organometallics
2010, 29, 2789–2795
160.-Javier Romero-Fernandez,
Fernando Carrillo-Hermosilla, Antonio Antiñolo,Carlos Alonso-Moreno,
Ana M.
Rodríguez, Isabel López-Solera and Antonio Otero
Oxo-
and imido-alkoxide vanadium complexes as precatalysts for the guanylation of
aromatic amines
Dalton Trans.,
2010, 39, 6419–6425
161.-
Antonio Antiñolo, Santiago García-Yuste,
Antonio Otero, Rebeca Reguillo-Carmona“An easy and direct synthetic
route to phosphamido niobocenes through nucleophilic attack of phosphide
niobocene complexes on acyl halides
C. R. Chimie 13 (2010) 929–934
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150.- S. Gómez-Ruiz, A.
Garcés, S. Prashar, M. Fajardo, A. Antiñolo, A. Otero,
Synthesis,characterization and applications in ethylene polymerization of
asymmetric ansa-titanocene complexes. Molecular structure of [Ti{Me2Si(η
5-C5Me4)(η 5-C5H3 iPr}Cl2],
Inorg. Chim.
Acta 2009,
362,
1042-1046
151.-
Antonio Antiñolo, Santiago García-Yuste, Antonio Otero, Rebeca
Reguillo-Carmona
“Insertion Reactions of
Isothiocyanates into the Nb–P Bond of Phosphide-Niobocene Complexes”.
Eur. J.
Inorg. Chem. 2009,
539-544
152.-Carlos Alonso-Moreno, José Sancho, Fernando
Carrillo-Hermosilla, Antonio Otero, Antonio Antiñolo, Isabel López-Solera
Synthesis,
Characterization and Compared Reactivity of Asymmetrical ansa-Metallocenes
Inorganic Chemistry Communications, 2009,12,
184-186
153.-
Antonio Otero , Juan Fernández-Baeza a, Antonio Antiñolo , Juan Tejeda ,
Agustín Lara-Sánchez a, Luis F. Sánchez-Barba, Margarita Sánchez-Molina ,
Carles Bo, Manuel Urbano-Cuadrado
Hybrid scorpionate/cyclopentadienyl titanium and zirconium complexes with
alkoxide and imido ligands
Inorganica
Chimica Acta 362 (2009) 2909–2914
154.-Carlos Alonso-Moreno, Fernando Carrillo-Hermosilla, Javier
Romero-Fernández, Ana M. Rodríguez, Antonio Otero, Antonio Antiñolo
Well-Defined Regioselective
Iminopyridine Rhodium Catalysts for Anti-Markovnikov Addition of Aromatic
Primary Amines to 1-Octyne
Adv. Synth. Catal. 2009, 351, 881 –
890
155.-
Javier Romero, Fernando Carrillo-Hermosilla, Antonio Antiñolo, Antonio
Otero
Homogeneous and supported bis(imino)pyridyl vanadium(III) catalysts
Journal of
Molecular Catalysis A: Chemical 304 (2009) 180–186
156.-Antonio Antiñolo ,
Rafael Fernández-Galán , Noelia Molina , Antonio Otero , Iván Rivilla ,Ana
M. Rodríguez
New
alkenyl-substituted group 4 C-ansa-metallocene complexes. Reactivity of the
substituent at the carbon ansa bridge
Journal of Organometallic
Chemistry 694 (2009) 1959–1970
157.-Carlos Alonso-Moreno,
Pedro Carrión, Fernando Carrillo-Hermosilla, Antonio Antiñolo and Antonio
Otero
UV–visible spectroscopy for zirconocene activation by MAO in olefin
polymerization: activity versus wavenumber
Appl. Organometal. Chem. 2009 , 23,
241–244
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145.-Antonio Otero, Juan
Fernández-Baeza, Antonio Antiñolo, Agustín Lara-Sánchez, Emilia
Martínez-Caballero, Juan Tejeda,Luis F. Sánchez-Barba, Carlos Alonso-Moreno,
and Isabel López-Solera
Scandium and Yttrium Complexes Supported by CNP Heteroscorpionate Ligands:
Synthesis, Structure, and Polymerization of e-Caprolactone
Organometallics
2008, 27, 976–983
146.- Pedro J. Aragón
Sáez, Fernando Carrillo-Hermosilla, Elena Villaseñor, Antonio Otero, Antonio
Antiñolo, and Ana M. Rodríguez
Heterocycle-Substituted Indenes as Precursors for Supported Zirconocene
Catalysts
Eur. J. Inorg. Chem. 2008,
330-337
147.- Carlos
Alonso-Moreno, Andrés Garcés, Luis F. Sánchez-Barba, Mariano Fajardo, Juan
Fernández-Baeza, Antonio Otero, Agustín Lara-Sánchez, A. Antiñolo, L.
Broomfield, M. I. López-Solera, and A. M. Rodríguez
Discrete Heteroscorpionate Lithium and Zinc Alkyl Complexes. Synthesis,
Structural Studies, and ROP of Cyclic Esters
Organometallics
2008, 27,
1310–1321
148.- Antonio Otero, Juan Fernández-Baeza, Agustín
Lara-Sánchez, Antonio Antiñolo, Juan Tejeda, Emilia Martínez-Caballero,
Isabel Márquez-Segovia, Isabel López-Solera, Luis F. Sánchez-Barba, and
Carlos Alonso-Moreno.
Versatile Scorpionates and New
Developments in the Denticity Changes of NNCp Hybrid Scorpionate/Cyclopentadienyl
Ligands in Sc and Y Compounds: From κ1-Nη5-Cp to κ2-NNη5-Cp
Inorg. Chem. 47(2008)4996
149. - Ortiz, M., Torréns,
M., Mola, J.L., Ortiz, P.J., Fragoso, A., Díaz, A., Cao, R., Prados, P., De
Mendoza, J., Otero, A., Antiñolo, A., Lara, A.
Nitric oxide binding and
photodelivery based on ruthenium (II) complexes of
4-arylazo-3,5-dimethylpyrazole
Dalton Transactions,
2008. 3559-3566
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134.-Santiago Gómez-Ruiz
a, Sanjiv
Prashar, Luis F. Sánchez-Barba, Dorian Polo-Cerón, Mariano Fajardo , Antonio
Antiñolo, Antonio Otero, Miguel A. Maestro, César J. Pastor
“Synthesis and catalytic
applications of C1 symmetric group 4 ansa-metallocene
complexes”
Journal of Molecular Catalysis A:
Chemical 264 (2007) 260–269
135.- Dorian Polo-Cerón
a, Santiago
Gómez-Ruiz a,
Sanjiv Prashar, Mariano Fajardo, Antonio Antiñolo, Antonio Otero, Isabel
López-Solera, Manuel L. Reyes.
“Synthesis of chiral unbridged
zirconocene complexes: Applications in the polymerization of ethylene and
propylene”
Journal of Molecular Catalysis A:
Chemical 268 (2007) 264–276
136.-
Antonio Otero, Juan Fernandez-Baeza, Antonio Antiñolo, Juan Tejeda, Agustin
Lara-Sánchez, Luis F. Sánchez-Barba, Isabel Lopez-Solera, and Ana M.
Rodriguez
“Lithium, Titanium, and Zirconium Complexes with Novel
Amidinate Scorpionate Ligands”
Inorg. Chem.
46(2007)1760-1770
137.- Antonio Antiñolo, Santiago
García-Yuste, Antonio Otero, Juan C. Pérez-Flores, Maria Isabel Lopez-Solera
, Ana M. Rodríguez,
“Reactivity of hydride-niobocenes towards heterocycles with hydroxide, -mercapto
or -amine functionalities. X-ray molecular structure of [(h5-C5H4SiMe3)2Nb(CNXylyl)2][I3]
and [(h5-C5H4SiMe3)2Nb(H)(P(OMe)3)]·(bzta)’-NH2.
((bzta)’-NH2=2-amino-6-methylbenzothiazol)”.
J.Organomet. Chem. 692 (2007) 3328–3339
138.-Dorian Polo-Cerón,
Santiago Gómez-Ruiz, Sanjiv Prashar, Mariano Fajardo, Antonio Antiñolo and
Antonio Otero
“Synthesis Of Bulky Zirconocene
Dichloride Compounds And Applications In Olefin Polymerization”
Collect. Czech. Commun.
2007, Vol. 72, Nos. 5–6, pp. 747–763
139.-Santiago Gómez-Ruiz a, Sanjiv Prashar, Mariano Fajardo, Antonio
Antiñolo, Antonio Otero.
Synthesis,
structural characterization and reactivity of new tin bridged
ansa-bis(cyclopentadiene) compounds: X-ray crystal
structures of Me2Sn(C5Me4R-1)2
(R = H, SiMe3)
J.Organomet. Chem. 692
(2007) 3057-3064
140.- Antonio Antiñolo, Santiago García-Yuste,
Antonio Otero, Elena Villaseñor
On the Insertion Processes of Unsaturated Molecules Into
Nb-X sigma Bond of Cp'2NbX Moieties ( Cp'=h5-C5H4SiMe3,
X= H, C, P)
J.Organomet. Chem.
692 (2007) 4436–4447
141.- Otero, A; Fernandez-Baeza,
J; Antiñolo, A; Tejeda, J; Lara-Sanchez, A; Sanchez-Barba, LF; Sanchez-Molina,
M; Rodriguez, AM; Bo, C; Urbano-Cuadrado, M
Expanding
heteroscorpionates. Facile synthesis of new hybrid scorpionate/cyclopentadienyl
ligands and their lithium and group 4 metal compounds: A combined
experimental and density functional theory study
Organometallics 2007,
26, 4310-4320
142.-Santiago Gómez-Ruiz, Dorian Polo-Cerón,
Sanjiv Prashar, Mariano Fajardo, Antonio Antiñolo, Antonio Otero
Synthesis and reactivity of
alkenyl substituted zirconocene complexes and their application as olefin
polymerization catalysts
Eur. J. Inorg. Chem. 2007,
4445–4455
143.- Otero, A., J.
Fernandez-Baeza, A. Antinolo, J. Tejeda, A. Lara-Sanchez, L. F. Sanchez-Barba,
M. Sanchez-Molina, S. Franco, M. I. Lopez-Solera, A. M. Rodriguez.
Highly
diastereoselective nucleophilic addition to myrtenal. Straightforward
synthesis of an enantiopure scorpionate ligand.
Inorg. Chem. 46(2007)8475-8477
144.-Luis F. Sanchez-Barba,
Andres Garcés, Mariano Fajardo, Carlos Alonso-Moreno, Juan Fernández-Baeza,
Antonio Otero, Antonio Antiñolo, Juan Tejeda, Agustín Lara-Sánchez, and
María I. López-Solera
Well-Defined Alkyl Heteroscorpionate Magnesium Complexes as Excellent
Initiators for the ROP of Cyclic Esters
Organometallics
2007, 26, 6403-6411
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122.- S. Prashar, A. Antiñolo, A.
Otero
“Insights into Group 4 and 5
ansa-Bis(cyclopentadienyl) Complexes with a single-atom bridge “
Coord. Chem. Rev.,
250 (2006) 133–154
123.-Antonio Otero, Juan Fernández-Baeza,
Antonio Antiñolo, Juan Tejeda, Agustín Lara-Sánchez, Luis Sánchez-Barba,
Margarita Sánchez-Molina, Sonia Franco, Isabel López-Solera, and Ana M.
Rodríguez
“A Simple and Efficient Synthetic
Route to Enantiopure Scorpionate Ligands”
Eur. J. Inorg. Chem. 2006,
707-710.
124.- Pedro J. Aragón,
Fernando Carrillo-Hermosilla, Elena Villaseñor,
Antonio Otero,
Antonio Antiñolo and Ana M. Rodríguez
“Synthesis, Structure and
Reactivity in Styrene Polymerization by Heterocyclic
Alkoxy- and Thiolatotitanium(IV)
Complexes”
Eur. J. Inorg. Chem. 2006,
965-971
125.- Carlos Alonso-Moreno, Antonio Antiñolo,
Fernando Carrillo-Hermosilla, Antonio Otero, Ana M. Rodríguez, José Sancho,
Victoria Volkis and Moris Eisen
Synthesis, characterization and
catalytic properties of ansa-zirconocenes [Zr{1-Me2Si(3-h5-C9H5R)2}Cl2]
(R = Me, nPr, nBu and Bz)
Eur. J. Inorg. Chem. 2006,
972-979
126.-Antonio Antiñolo, Santiago García-Yuste, Antonio
Otero, Juan C. Pérez-Flores, Rebeca Reguillo-Carmona, Ana M. Rodríguez,
Elena Villaseñor
“Reactivity of a Phosphido-Niobocene
Derivative Toward CS2 and Alkyl Halides to Give
Phosphinodithioformato- and Phosphino-Niobocene Complexes; X-ray Crystal
Structures of [Nb(h5-C5H4SiMe3)2(k1-S-SC(S)(PPh2))(CO)]
and [Nb(h5-C5H4SiMe3)2(P(I)Ph2)(CO)]I3”
Organometallics
2006, 25, 1310-1316
127.- Antonio Antiñolo,
Iván Dorado, Mariano Fajardo, Andrés Garcés, Marek M. Kubicki , Carmen
López-Mardomingo, Antonio Otero, Sanjiv Prashar
Synthesis and
reactivity of new mono and dinuclear niobium and tantalum imido complexes:
X-ray crystal structure of [Ta(η5-C5H4SiMe3)Cl2{=NC6Me4-4-(N(SiMe3)2)}]
J.Organomet. Chem. 691 (2006)
1361–1368
128.-Antonio Antiñolo, Santiago
García-Yuste, Maria Isabel Lopez-Solera, Antonio Otero, Juan C.
Pérez-Flores, Rebeca Reguillo-Carmona, Elena Villaseñor
“Activation of a CNXylyl ancillary
ligand in the reaction of electron-deficient alkynes with a phosphido
niobocene complex. X-ray Crystal Structure of [Nb(h5-C5H4SiMe3)2(h1-C-k1-P-C(=N(Xylyl))C(CO2Me)C(H)PPh2)]”
Dalton Trans. 2006,
1495-1496
129.-Synthesis and reactivity of asymmetrically substituted ansa-bridged
zirconocene complexes. X-ray crystal structures of [Zr{R(H)C(h5-C5Me4)(h5-C5H4)}Cl2]
(R = Bun, But) and [Zr{Bun(H)C(h5-C5Me4)(h5-C5H4)}(CH2Ph)2]
J. Organomet. Chem. 691,
2006, 2924-2932
130. Antonio Antiñolo, David
Evrard, Santiago García-Yuste, Antonio Otero, Juan C. Pérez-Flores, Rebeca
Reguillo-Carmona, Ana M. Rodríguez, Elena Villaseñor
Synthesis, Reactivity and X-Ray
Diffraction Structures of New Isocyanideniobocene Complexes: [Nb(h5-C5H4SiMe3)2(CNR)(PMePh2)]X,
R=Xylyl, Cy and [Nb(h5-C5H4SiMe3)2(P(I)Ph2)(CNXylyl)]I3
Organometallics 2006, 25, 3698-3705
131.- Andrés Garcés,
Yolanda Pérez , Santiago Gómez-Ruiz, Mariano Fajardo , Antonio Antiñolo ,
Antonio Otero , Carmen López-Mardomingo , Pilar Gómez-Sal , Sanjiv Prashar,
“Synthesis
of Niobocene Imido Cations. X-ray crystal structure of [Nb(=NBut)(η5-C5H4SiMe3)2(CNBut)][BPh4]”
J.Organomet. Chem.
691, 2006, 3652-3658
132.- Pedro Carrión, Fernando
Carrillo-Hermosilla, Carlos Alonso-Moreno, Antonio Otero, Antonio
Antiñolo, José Sancho, Elena Villaseñor
“Supported modified zirconocene catalyst for ethylene polymerization.”
Journal of Molecular Catalysis A: Chemical 258(2006)236-245
133.- Antonio Otero, Juan
Fernández-Baeza, Antonio Antiñolo, Juan Tejeda, Agustin Lara-Sánchez, Luis
Sánchez-Barba, Margarita Sánchez-Molina, Sonia Franco, Isabel López-Solera
and Ana M. Rodríguez
“Design
of new heteroscorpionate ligands and their coordinative ability toward Group
4 transition metals; an efficient synthetic route to obtain enantiopure
ligands”
Dalton Trans. 2006, 4359-4370
105.-Antonio Otero, Juan Fernández-Baeza,
Antonio Antiñolo, Juan Tejeda,
Agustín Lara-Sánchez, Luis Sánchez-Barba, and
Ana M. Rodríguez
“New Complexes of Niobium(V) and
Tantalum(V) with Monoanionic NNO Heteroscorpionate Ligands”
Eur. J. Inorg.
Chem. 2004, 260
117.-
Antonio Antiñolo, Santiago García-Yuste, Isabel López-Solera, Antonio Otero,
Juan Carlos Perez-Flores, Isabel del Hierro, Laurent Salvi, Helene Cattey,
Yves Mugnier
“New reactivity of Cp’2NbH3; Cp’ C5H4SiMe3.
Synthesis, electrosynthesis and reactivity of new carboxylato niobocene
complexes”
J.Organomet. Chem.
690 (2005) 3134–3141
118.-
Santiago Gómez-Ruiz, Sanjiv Prashar, Mariano Fajardo,
Antonio Antiñolo, Antonio Otero, Miguel A. Maestro,
Victoria Volkis, Moris S. Eisen d, César J. Pastor.
'Synthesis, hydrosilylation reactivity and catalytic
properties of group 4 ansa-metallocene complexes'
Polyhedron 24 (2005)
1298–1313
119.- Carlos Alonso-Moreno,Antonio
Antiñolo, Fernando Carrillo-Hermosilla, Pedro Carrión, Isabel López-Solera,
Antonio Otero, Sanjiv Prashar, and José Sancho
“Novel Indenylzirconium Complexes as Supported Catalysts
in the Polymerization of Ethylene”
Eur. J. Inorg. Chem. 2005, 2924-2934
120.-Antonio Otero, Juan Fernández-Baeza, Antonio Antiñolo, Juan Tejeda,
Agustín Lara-Sánchez, Luis Sánchez-Barba, Emilia Martínez-Caballero, Ana M.
Rodríguez, and Isabel López-Solera
“First Complexes of Scandium and Yttrium with NNO and NNS
Heteroscorpionate Ligands”
Inorg. Chem. 44(2005)5336
121.-
Mayreli Ortiz, Ariadna Penabad, Alicia Díaz, Roberto Cao, Antonio Otero,
Antonio Antiñolo, and Agustín Lara.
“Ruthenium Complexes of the
Scorpionate Ligand Bis (3,5-dimethylpyrazol-1-yl)-dithio acetate and the
Effect of Nitric Oxide Coordination”
Eur. J. Inorg. Chem. 2005,
3135-3140.
106.-
Iván Dorado, Andrés Garcés, Isabel López-Solera, Marek
Kubicki, Carmen López-Mardomingo, Mariano Fajardo, Antonio Antiñolo, Antonio
Otero
Synthesis, Structural Characterisation and Reactivity of
New Dinuclear Monocyclopentadienyl Imidoniobium and -tantalum Complexes.
Crystal and molecular structures of [{Nb(h5-C5H4SiMe3)Cl2}2(m-1,4-NC6H4N)],
[{Ta(h5-C5Me5)Cl2}2(m-1,4-NC6H4N)],
[{Nb(h5-C5H4SiMe3)(CH2C6H5)2}2(m-1,4-NC6H4N)]
and [{Ta(h5-C5Me5)(CH2SiMe3)2}2(m-1,4-NC6H4N)]
Eur. J. Inorg. Chem. 2004,1299
107.-Antonio
Otero, Juan Fernández-Baeza, Antonio Antiñolo, Juan Tejeda, Agustín
Lara-Sánchez, Luis Sánchez-Barba, Ana M. Rodríguez, and Miguel A. Maestro
“An Unprecedented Hybrid Scorpionate/Cyclopentadienyl
Ligand”
J.Am.Chem.Soc.
126(2004)1330
108.-A. Otero, J.
Fernández-Baeza, A. Antiñolo, J. Tejeda, A. Lara-Sánchez, M.
Fernández-López, and I. López-Solera
“New
Complexes of Zirconium(IV) and Hafnium(IV) with Heteroscorpionate Ligands
and the Hydrolysis of Such Complexes To Give a Zirconium Cluster”
Inorg. Chem. 43(2004)1350
109.- Iván
Dorado, Andrés Garcés, Isabel López-Solera, Marek Kubicki, Carmen López-Mardomingo,
Mariano Fajardo, Antonio Antiñolo, Antonio Otero
“Isocyanide insertion reactivity of dinuclear niobium and tantalum imido
complexes. X-ray crystal structure of [{Nb(h5-C5H4SiMe3)(CH2Ph)2}2(m-1,4-NC6H4N)]'
J.Organomet. Chem. 689(2004)1304
110.-A.
Otero, J. Fernández-Baeza, A. Antiñolo, J. Tejeda and A. Lara-Sánchez
“Heteroscorpionate ligands based on bis(pyrazol-1-yl)methane: design and
coordination chemistry”
J.Chem. Soc. Dalton Trans.
2004, 1499-1510
111.-
Mayreli Ortiz, Alicia Díaz, Roberto
Cao, Reynier Suardíaz, Antonio Otero,Antonio Antiñolo, and Juan
Fernández-Baeza
“Ruthenium Nitrosyl Complexes of
Bis(3,5-dimethylpyrazol-1-yl)methane Oxyanions”
Eur. J. Inorg. Chem. 2004,3353-3357
112.-Alonso, Carlos;
Antiñolo, Antonio; Carrillo-Hermosilla, Fernando; Carrión, Pedro; Otero,
Antonio; Sancho, Jose; Villaseñor, Elena.
“Modified silicas as supports for single-site zirconocene catalysts.”
Journal of Molecular Catalysis A: Chemical (2004), 220(2), 285-295.
113.- Antonio Antiñolo, Mariano
Fajardo, Santiago Gómez-Ruiz, Isabel López-Solera, Antonio Otero, Sanjiv
Prashar
“Hydrosilylation in the Design and
Functionalization of ansa-Metallocene Complexes”
Organometallics 2004,23,4062-4069.
114.- Antonio Antiñolo,
Rafael Fernández-Galan, Antonio Otero, Sanjiv Prashar, Ivan Rivilla, Ana M.
Rodríguez, Miguel Maestro
“New Synthon in the Desing of
ansa-Cyclopentadienyl Ligands with Variable Substitution at the Bridging
Atom. New ansa-Zirconocene
Complexes”
Organometallics 2004,23, 5108-5111.
115.- Laurent Salvi, Alain Vallat, Helene
Cattey, Yves Mugnier, Antonio Antinolo,
Antonio Otero, Santiago
Garcıa-Yuste
“Electron-transfer-catalyzed ligand substitution of carboxylato niobocene
complex induced by electrochemical oxidation”
J.Organomet. Chem. 689 (2004) 3473–3480
116.- A. Otero, J. Fernández-Baeza, A. Antiñolo, J.
Tejeda, A. Lara-Sánchez, L. Sánchez-Barba y A. M. Rodríguez.
“Titanium and niobium imido
complexes stabilized by heteroscorpionate ligands.”
J.Chem. Soc. Dalton Trans.
2004, 3963-3969
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97.- Antonio Antiñolo, Mariano Fajardo, Antonio Otero and Sanjiv Prashar.
“Sandwich and Half Sandwich Niobium
Imido Complexes”
Eur. J. Inorg. Chem. 2003, 17
98.-
Antonio Antiñolo, Cristina García-Yebra, Mariano Fajardo, Isabel del Hierro,
Carmen López-Mardomingo, Isabel López-Solera, Antonio Otero, Yolanda Pérez
and Sanjiv Prashar
“Síntesis and Reactivity of Alkynyl
niobiocene complexes”
J.Organomet. Chem. 670(2003)123
99.-
Antonio Antiñolo, Iván Dorado, Mariano Fajardo, Andrés
Garcés, Marek M. Kubicki, Carmen López-Mardomingo and Antonio Otero
“Synthesis and structural
characterisation of new organo-diimido tantalum and niobium complexes”
J.Chem. Soc. Dalton Trans.
2003, 910
100.-A. Otero, J. Fernández-Baeza, A. Antiñolo,
J. Tejeda, A. Lara-Sánchez, L. Sánchez-Barba, M. T. Expósito, A. M.
Rodríguez
“Niobium complexes containing a new
chiral heteroscorpionate ligand and the reactivity of such a complex with O2
to give the first gem-diolate niobium complex”
J.Chem. Soc.
Dalton Trans. 2003, 1614
101.-I. del Hierro, R.
Fernández-Galán, S. Prashar, A. Antiñolo, M. Fajardo, A.M. Rodríguez, A.
Otero
The Reactivity Allyl and
Olefin-Hydride Niobocene Derivatives Towards Isocyanides. X-ray Crystal
Structure of [Nb(h5-C5H4SiMe3)2(h3-CHRCHCHR)]
(R = SiMe2tBu)
Eur. J. Inorg. Chem. 2003, 2438
102.-A. Antiñolo, R.
Fernández-Galán, B. Gallego, A. Otero, S. Prashar, A.M. Rodríguez
Synthesis and Reactivity of Alkyl
Zirconium Complexes Incorporating Asymmetrically Substituted ansa-Ligands.
X-ray Crystal Structure of [Me2Si(h5-C5Me4)(h5-C5H3Me)]Zr(CH2Ph)Cl
Eur. J. Inorg. Chem. 2003, 2626
103.-
Antonio Otero, Fernando
Carrillo-Hermosilla, Pilar Terreros, Teresa Exposito, Sergio Rojas, Juan
Fernandez-Baeza, Antonio Antiñolo, and Isabel Lopez-Solera
“Synthesis, Structure and
Reactivity of New Late Transition Metal Complexes Bearing Diphosphane
Ligands Derived from Bis(pyrazol-1-yl)methane”
Eur. J. Inorg. Chem. 2003, 3233
104.-A. Antiñolo, M. Fajardo, S.
Gómez-Ruiz, I. López-Solera, A. Otero, S. Prashar, A.M. Rodríguez ”Group 4
Metallocene Complexes Incorporating Vinyl or Allyl Substituted ansa
Ligands. X-ray Crystal Structures of
[Zr{Me(CH2=CH)Si(h5-C5Me4)2}Cl2],
[Zr{Me(CH2=CHCH2)Si(h5-C5H4)2}Cl2]
and [Zr{Me(CH2=CHCH2)Si(h5-C5Me4)(h5-C5H4)}Cl2]”
J.Organomet. Chem. 683 (2003) 11
|
|
91.-
Jorge Moniz Santos, Maria Rosario Ribeiro, Manuel Farinha Portela, Henri
Cramail, Alain Deffieux, Antonio Antiñolo, Antonio Otero, Sanjiv Prashar
“[(h5-C5Me4)SiMe2(NtertBu)]TiCl2
as Pre-Catalyst for the Copolymerisation of Ethylene with
5,7-Dimethylocta-1,6-diene and with 3,7-Dimethylocta-1,6-diene”
Macromol. Chem. Phys. 2002, 203, 139-145
92.-Carlos Alonso-Moreno, Antonio Antiñolo, Isabel
López-Solera, Antonio Otero, Sanjiv Prashar, Ana M. Rodríguez, Elena
Villaseñor.
“Niobium, Titanium and Hafnium
Complexes Incorporating Bridges ansa ligand. X-Ray Crystal
Structures of [Zr{Me2Ge(h
5-C5Me4)2}Cl2
and [M{Me2Si(h 5
-C5Me4)(h 5 -C5H4)}
Cl2] (M= Zr, Hf)”
J.Organomet. Chem. 656(2002)129-138
93.-Antonio Antiñolo, Rafael Férnandez-Galan, Irache
Orive, Antonio Otero, Sanjiv Prashar
“New Group 4 Metallocene and
Niobiocene Complexes Containing Phosphine Functionalized ansa-ligands”
Eur. J. inorg. Chem. 2002
2470-2476
94.-Antonio Antiñolo, Isabel
López-Solera, Antonio Otero, Sanjiv prashar, Ana M. Rodríguez and Elena
Villaseñor.
Reactivity of Zirconium Complexes Incorporating Asymmetrically Substituted
ansa Ligands and their use as Catalyst in Olefin Polymerization.
X-Ray Crystal Structure of
[Me2Si(h
5
-C5Me4)(h
5
-C5H3R)]ZrCl2 (R) Et, iPr)”
Organometallics 2002,21,2460-2467
95.- Antonio Antiñolo, Teresa Expósito, Isabel del Hierro, Dominique Lucas,
Yves Mugnier, Irache Orive, Antonio otero, Sanjiv Prashar
Synthesis and Electrochemistry of
Niobiun Complexes Incorporating Asymmetrically Subtituted ansa
Ligands.
J.Organomet. Chem. 655(2002)63-69
96.- Otero, A; Fernández-Baeza, J; Antiñolo, A; Carrillo-Hermosilla,
F; Tejeda, J; Lara-Sánchez, A; Sánchez-Barba, L; Fernández-López, M;
Rodríguez, AM; López-Solera, I
“Preparation of new monoanionic "scorpionate" ligands: Synthesis and
structural characterization of titanium(IV) complexes bearing this class of
ligand”
Inorganic
Chemistry, 41 (2002)5193-5202
89.-
Otero A. Fernández-Baeza J. Antiñolo A. Carrillo-Hermosilla F. Tejeda J.
Lara-Sánchez A. Lopez-Solera I.
“Synthesis and
spectroscopic characterization of alpha-keto ylide-containing Group 4 metal
complexes. The X-ray molecular structure of [Cp*ZrCl3(2-TCMP)],
Cp* = h5-C5Me5,
2-TCMP = [{2-thiazolylcarbonyl}methylene]triphenylphosphorane”
J. Organomet. Chem. 629,
2001, 68-76
90.-
Antonio Antiñolo, Isabel López-Solera, Antonio Otero y Sanjiv Prashar
“The synthesis
of alkyl niobocene imido complexes and the X-ray crystal structure of
[Nb(O)Cp2Me](Cp=5-C5H5)”
Journal of Organometallic
Chemistry, 631, 2001, 151
|
| I. DORADO, A. GARCÉS, C. LÓPEZ-MARDOMINGO, M. FAJARDO,
A. RODRÍGUEZ, A. ANTIÑOLO, A. OTERO
Synthesis and structural characterización of new organo-diimido and organo-imido
niobium and titanium complexes
J. Chem. Soc., Dalton Trans., 2375-2382, (2000).
|
| C. GARCÍA-YEBRA, C. LÓPEZ-MARDOMINGO, M. FAJARDO, A.
ANTIÑOLO, A. OTERO, A. RODRÍGUEZ, A. VALLAT, D. LUCAS, Y MUGNIER, J.J. CARBÓ,
A. LLEDÓS, C. BO
Facile synthesis of alkynyl- and vinylidene-niobocene complexes. Unexpected
h1-vinylidene-h2-alkyne
isomerization
Organometallics, 19: 1749-1765, (2000).
|
| A. ANTIÑOLO, I. DEL HIERRO, I. LÓPEZ-SOLERA, S.
GARCÍA-YUSTE, A. OTERO, M. FAJARDO, A. RODRÍGUEZ
Synthesis and reactivity of new oxo alkyl or oxo acyl niobocene complexes
and crystal structure of Cp'2Nb(=O(OC(O)CF3)(Cp'=h5-C5H4SiMe3)
Journal of Organometallic Chemistry, 598: 167-173, (2000).
|
| C. GARCÍA-YEBRA, F. CARRERO, C. LÓPEZ-MARDOMINGO, M.
FAJARDO, A. RODRÍGUEZ, A. ANTIÑOLO, A. OTERO, D. LUCAS, I. MUGNIER
New niobocene alkyne complexes: synthesis and characterization of neutral
and cationic niobium complexes with functionalized alkynes.
X-ray crystal structure of [Nb(? 5- C5H4SiMe3)2(Cl)(? 2(C,C)-R1C? CR2)](R1 =
C? CPh, R2 = Ph (2b); R1 = CH2CH=C(CH3)2, R2 = Ph (3b)
Organometallics, 18: 1287-1298, (1999)
|
| A. ANTIÑOLO, M. FAJARDO, C. HUERTA,
A. OTERO, S. PRASHAR, A. M. RODRÍGUEZ
Sandwich and half-sandwich niobium imido complexes: X-ray crystal structure
of [Nb(=NAr)Cp'2Cl] (Cp' =
h5-C5H4SiMe3, Ar = C6H4OMe-4)
Journal of Organometallic Chemistry, 585:
154-161, (1999)
|
| C. GARCÍA-YEBRA, A. ANTIÑOLO, F.
CARRILLO-HERMOSILLA, M. FAJARDO, J. FERNÁNDEZ-BAEZA, S. GARCÍA-YUSTA, A. OTERO
Advances in the chemistry of bis-cyclopentadienyl hydride derivatives of
niobium and tantalum.
Coord. Chem. Rev., 193 (195):43-72, (1999)
|
| Z. M. TEHRANI, D. LUCAS, Y. MUGNIER,
A. ANTIÑOLO, A. OTERO, M. FAJARDO, A. GARCÉS, C. LÓPEZ-MARDOMINGO
Electrocatalytic process in the reduction of {Nb[h5-C5H4(SiMe3)]2(Cl)(NHPh)}BF4
Journal of Organometallic Chemistry,
548:309-313, (1997)
|
| A. ANTIÑOLO, F. CARRILLO-HERMOSILLA,
A. OTERO, M. FAJARDO, A. GARCÉS, P. GÓMEZ-SAL, C. LÓPEZ-MARDOMINGO, A. MARTÍN,
C. MIRANDA
Synthesis and structural characterization of isocyanate, amido and imido
niobocene derivatives:crystal structures of [Nb(h5-C5H4SiMe3)2Cl(k2N,C-OCNPh]
and [{Nb(h5-C5H4SiMe3)2Cl}2-(m-1,3-N2C6H4)
J. Chem. Soc., Dalton Trans., 59-65, (1998)
|
| A. ANTIÑOLO, F. CARRILLO-HERMOSILLA,
A. CASTEL, M. FAJARDO, J. FERNÁNDEZ-BAEZA, M. LANFRANCHI, A. OTERO, M. A.
PELLINGHELLI, G. RIMA, J. SATGÉ, E. VILLASEÑOR
Synthesis and characterization of the first niobocene germyl complexes and
reactivity of triphenylsilyl-, triphenylgermyl-, and triphenylstannylniobocene
derivatives. X-ray molecular structures of d0 Nb(h5-C5H4SiMe3)2(H)2(EPh3)
(E = Ge, Sn)
Organometallics, 17:1523-1529, (1998)
|
| A. Antiñolo; F. Carrillo-Hermosilla; S. García-Yuste; M.
Freitas; A. Otero; S. Prashar; E. Villaseñor; M. Fajardo
Inorg. Chim. Acta 1997, 259, 101-105.
Insertion reactions of heterocumulenes into the niobium-hydride bond of
isocyanide and carbonyl niobocene complexes
The reaction of the hydride niobocene complexes, Nb(eta(5)- C5H4SiMe3)(2)(H) (CNR)
(R = 2,6-dimethylphenyl (Xylyl) orcyclohexyl (Cy)) and Nb(eta(5)-C5H4SiMe3)(2)(H)(CO)
with the heterocumulenes PhN = C = X (X = O or S) affords the new formamido
and thioformamido complexes Nb(eta(5)-C5H4SiMe3)(2)(CNR) (eta(1)-XC(H)NPh) (R
= Xylyl, X = O (1); R=Xylyl, X = S (2); R = Cy, X = O (3); R = Cy, X = S (4))
and Nb(eta(5)-C5H4SiMe3)(2)(CO) (eta(1)-XC(H)NPh) (X = O (5); X = S (6)).
The protonation of these derivatives using HCF3COO yields
the trifluoroacetato complexes Nb(eta(5)-C5H4SiMe3)(2)(CNR) (eta(1)- OOCCF3)
(R = Xylyl (7); R = Cy (8)) and Nb(eta(5)-C5H4SiMe3)(2)(CO) (eta(1). OOCCF3)
(9) and the imine derivatives HOC(H) = NPh and HSC(H) = NPh. Thermal treatment
of 5 gives the eta(2)-formamido complex
Nb(eta(5)-C5H4SiMe3)(2)(eta(2)-OC(H)NPh) (10). All these complexes have
been characterised by spectroscopic methods.
|
| A. Antiñolo; F. Carrillo-Hermosilla; M. Fajardo; S.
García-Yuste; A. Otero; S. Camanyes; F. Maseras; M. Moreno; A. Lledós; J. M.
Lluch
J. Am. Chem. Soc.
1997, 119, 6107-6114.
Synthesis and Spectroscopic Properties of Dihydrogen Isocyanide Niobocene [Nb(h5-C5H4SiMe3)2(h2-H2)(CNR)]+
Complexes. Experimental and Theroretical Study of the Blocked Rotation of a
Coordinated Dihydrogen
Synthesis of stable hydride isocyanide derivatives Nb(eta(5)- C5H4SiMe3)(2)(H)(CNR)
has been achieved through the formation of coordinatively unsaturated
16-electron species Nb(eta(5)- C5H4SiMe3)(2)H by thermolytic loss of H-2
followed by the coordination of an isocyanide ligand. Low-temperature
protonation with a slight excess of CF3COOH leads to the eta(2)-dihydrogen
complexes [Nb(eta(5)-C5H4SiMe3)(2)(eta(2)-H-2)(CNR)](+). NMR spectra of these
H-H complexes and their monodeuterated H-D isotopomers present a single
high-field resonance at room temperature. By lowering the temperature to 178
K, decoalescence of the signal was observed for the H-D complexes but not for
the H-H ones. By combining DFT electronic structure calculations with a
monodimensional rotational tunneling model, it has been shown that the absence
of decoalescence of the H-H signal is due to the existence of a very large
exchange coupling. Conversely, for the H-D isotopomer, the difference in zero
point energy corresponding to two nonequivalent (H- D and D-H) positions leads
to a slight asymmetry which dramatically reduces the exchange coupling,
allowing decoalescence to be observed. Therefore, the H-D classical rotation
and the quantum exchange processes will not be practically observed for this
complex, whereas only the classical process for the H-H species is quenched
out on the NMR time scale.
|
| A. Antiñolo; A. Otero; M. Fajardo; R. Gil-Sanz; M. J.
Herranz; C. López-Mardomingo; A. Martín; P. Gómez-Sal
J. Organomet. Chem.
1997, 533, 87-96.
Synthesis, structure, and chemistry of hydrido and alkyl niobocene Ketene
and Ketenimine derivatives. X-ray crystal structure of [Nb(h5-C5H4SiMe3)2(CH3)(h2-(C,O)O=C=CPh2)]
[Nb(eta(5)-C5H4SiMe3)(2)Cl(eta(2)-(C,Z)-ZCCRPh)] (1a, Z = NPh, R = Ph; 1b, Z =
NPh, R = Me; 1c, Z = NPh, R = Et; 1d, Z = NPh, R = H; 2, Z = O, R = Ph) reacts
with Li(BEt3H) and with Grignard (RMgI) or dialkyl magnesium (R2Mg) reagents
to give the hydride niobocene complexes [Nb(eta(5)-C5H4SiMe3)(2) H(eta(2)-(C,Z)-ZCCRPh)]
(3a, Z = NPh, R = Ph; 3b, Z = NPh, R = Me; 3c, Z = NPh, R = Et; 3d, Z = NPh, R
= H, 4, Z = O, R = Ph) and the alkyl niobocene complexes [Nb(eta(5)-
C5H4SiMe3)(2)R(eta(2)-(C,Z)-ZCCR'Ph) (5a, Z = NPh, R = Me, R' = Ph; 5b, Z =
NPh, R = R' = Me; 5c, Z = NPh, R = Me, R' = Et; 5d, Z = NPh, R = Me, R' = H;
6a, Z = O, R = Me, R' = Ph; 6b, Z = O, R = Et, R' = Ph) respectively. The
molecular structure of 6a was determined by single-crystal diffractometry. It
shows a typical bent-metallocene geometry around the niobium atom with the
eta(2)(C,O) ketene and methyl groups arrayed in the plane between the two
cyclopentadienyl rings. Finally, some hydride and alkyl niobocene ketenimine
and ketene complexes were easily protonated with 1 equiv. Of HBF4 . OEt2
giving rise, in one step, to the corresponding eta(2)-iminoacyl and
eta(2)-acyl complexes [Nb(eta(5)-C5H4SiMe3)(2)Y(eta(2)-(C,Z)- ZCCRHPh)](+)
+[BF4-] (7a, Y = H, Z = NPh, R = Ph; 7b, Y = H, Z = NPh, R = Me; 8a, Y = Me, Z
= NPh, R = Ph; 8b, Y = Me, Z = NPh, R = Et; 9, Y = Me, Z = O, R = Ph). H-1 NMR
studies on several unsymmetrical ketenimine-bearing chloro, hydride and methyl
niobocene complexes containing E-Z isomeric mixtures were carried out, and it
was found that intermolecular isomerization of the E and Z isomers may govern
the different observed E-Z ratios. The structures of the different families of
complexes were determined by spectroscopic methods.
|
| A. Antiñolo; F. Carrillo-Hermosilla; I. D. Hierro; A.
Otero; M. Fajardo; Y. Mugnier
Organometallics 1997, 16, 4161-4166.
Synthesis and Characterization of New Alkyl-Carbon
Dioxide Compounds and the First Neutral Acyl-Carbonyl Niobocene Complexes
The olefin-hydride complexes Cp-2'Nb(H)(eta(2)-RHC=CH2) (Cp' = eta(5)-
C5H4SiMe3; R = H (3), C6H5 (4, endo isomer)) were prepared by the alkylation
reactions of [Cp-2'NbCl](2) (1) with the appropriate Grignard reagents RMgX (R
= CH2CH3, CH2CH2C6H5) followed by a stereoselective beta-elimination from the
intermediate alkyl complexes Cp-2'Nb(CH2CH2R). Complexes
Cp-2'Nb(H)(eta(2)-RHC=CH2) (R = C6H4CH3 (5), C6H4OCH3 (6)) were prepared as a
mixture of endo and exo isomers by reaction of Cp-2'NbH3 (2) with the
corresponding olefin. Furthermore, reactions of CO with 3 and 4, and the
reactions of CO2 with 3-6, afforded the alkylniobocene complexes Cp-2'Nb(CO)R
(R = CH2CH3 (7), CH2CH2C6H5 (8)) Cp-2'Nb(eta(2)-CO2)(R) (R = CH2CH3 (9)),
CH2CH2C6H5 (10), CH2CH2C6H4CH3 (11), CH2CH2C6H4OCH3 (12)). The reactivity of 9
and 10 toward the strong Lewis acid B(C6F5)(3) was also studied; in a first
step the adducts Cp-2'Nb(eta(2)-CO2- B(C6F5)(3))(CH2CH2R) (R = H (13), C6H5
(14)) were formed and subsequently evolved to give the oxo-alkyl complexes
Cp-2'Nb(O- B(C6F5)(3))(CH2CH2R) (R = H (15), C6H5 (16)) with the loss of CO.
Finally, reactions of 3 and 4 with CO under appropriate conditions gave the
neutral acylniobocene complexes Cp-2'Nb(CO)(eta(1)- C(O)CH2CH2R) (R = H (17),
C6H5 (18)), which were alternatively prepared from the reactions of 7 and 8
with CO. The different complexes were characterized by spectroscopic
methods.
|
| A. Antiñolo; A. Otero; M. Fajardo; C. García-Yebra; C.
López-Mardomingo; A. Martín; P. Gómez-Sal
Organometallics 1997, 16, 2601-2611.
Niobocene Alkyne Complexes: Synthesis and
Characterization of Neutral and Cationic d2 Metal Alkyne
Derivatives. X-ray Crystal Structure of [Nb(h5-C5H4SiMe3)2(h2(C,C)-HC=CPh)(CH2Ph)]
The paramagnetic niobocene alkyne complexes Nb(eta(5)- C5H4SiMe3)(2)(eta(2)(C,C)-RC=CR')
(2) have been synthesized from Nb(eta(5)-C5H4SiMe3)(2)(eta(2)(C,C)-RC=CR')(Cl)
(1) and subsequently oxidized in the presence of different ligands to give
stable cationic d(2) derivatives, [Nb(eta(5)C(5)H(4)SiMe(3))(2)(eta(2)(C,C)-
RC=CR')(L)][BPh4] (L = CH3CN, R = R' = Ph (3a); L = CH3CN, R = R' = CO2Me
(3b); L = CH3CN, R = R' = Me (3c); L = CH3CN, R = Me, R' = CO2Me (3d); L =
tBuCN, R = R' = Ph (4a); L = tBuCN, R = R' = CO2Me (4b); L = tBuCN, R = R' =
Me (4c); L = tBuCN, R = Me, R' = CO2Me (4d); L = tBuNC, R = R' = Ph (5a); L =
tBuNC, R = R' = CO2Me (5b); L = tBuNC, R = R' = Me (5c); L = THF, R = R' = Me
(6c); L = THF, R = Me, R' = CO2Me (6d); L = Py, R = R' = Ph (7a); L = Py, R =
R' = Me (7c)). Oxidation of the complex Nb(eta(5)-C5H4SiMe3)(2)(eta(2)(C,C)-
MeC=CCO2Me) (2d) under different experimental conditions gave rise to the
divinylidene binuclear d(2) niobocene complex [(eta(5)-
C5H4SiMe3)(2)(CO)Nb=C=C(CH3)(CH3)C=C=Nb(CO)(eta(5)- C5H4SiMe3)(2)][BPh4](2)
(8a). A mechanism involving the intermediacy of a sigma-acetylide species is
proposed for the formation of this compound. Thus, the divinylidene
complex [(eta(5)-
|
| A. Antiñolo; F. Carrillo-Hermosilla; B. Chaudret; M.
Fajardo; J. Fernández-Baeza; M. Lanfranchi; H. H. Limbach; M. Maurer; A.
Otero; M. A. Pellinghelli
Inorg. Chem. 1996, 35, 7873-7881.
Exchange Coupling in Niobocene Trihydrides, Nb(C5H3RR')2H3,
and Their Adducts with Copper Triad Cations, [{Nb(C5H3RR')2H3}2M]+
(R=R'=H; R=H,R'=SiMe3, R=R'=SiMe3; M=Cu, Ag, Au)
The reactions of Nb(C(5)H(3)RR')(2)Cl-2 with Red-Al followed by hydrolysis
yield Nb(C(5)H(3)RR')(2)H-3 (R = R' = H, 1; R = H, R' = SiMe(3), 2; R = R' =
SiMe(3), 3). These compounds react with Lewis acidic
coinage cationic species, namely, [Cu(MeCN)(4)]PF6, AgBF4, and ''Au(THT)PF6'',
prepared in situ from AuCl(THT) and TIPF6 in a 2 to 1 ratio to yield the
adducts [{Nb(C(5)H(3)RR')(2)H-3}(2)M](+) (M = Cu, R = R' = H, 7; R = H, R' =
SiMe(3), 8; R = R' = SiMe(3), 9; M = Ag, R = H, R' = SiMe(3), 10; R = R' =
SiMe(3), 11; M = Au, R = R' = H, 12; R = H, R' = SiMe(3), 13; R = R' =
SiMe(3), 14). Like 1, but unlike the corresponding tantalum derivatives
Ta(C(5)H(3)RR')(2)H-3 (R = R' = H, 4; R = H, R' = SiMe(3), 5; R = R' =
SiMe(3), 6), 2 and 3 show exchange couplings in their high-field H-1 NMR
spectra due to a hydride tunneling phenomenon. The magnitudes of exchange
couplings are larger in the cases of 2 and 3 than in the case of 1 as a result
of the decrease of electron density upon increasing the number of SiMe(3)
substituents on the Cp ring. The addition of a Lewis acidic cation results in
the observation of an AB(2) pattern for the hydrides at room temperature,
which splits at low temperature into an ABC one in agreement with a fluxional
behavior of the cation which binds to two hydrides of each niobium center. The
activation energy of these fluxional processes are close to 42-45 kJ . mol(-1)
in the case of Cu adducts, 37 kJ . mol(-1) in the case of Ag adducts, and 40
kJ . mol(-1) in the case of Au adducts. The magnitude of exchange couplings is
reduced upon addition of copper cation to 1-3, is of the same order of
magnitude after addition of a silver cation, and is greatly increased by
addition of a gold cation. A model is proposed to explain these variations
which involves two isomeric states that are close in energy, one involving two
bridging and one terminal hydrides on niobium and one involving one bridging
hydride and a dihydrogen molecule. A line shape analysis experiment carried
out on 14 allows determination of the parameters of the classical exchange,
the coupling constants at various temperatures which reach 550 Hz at 347 K,
and the parameters of the quantum mechanical exchange according to our
proposed model. The structure of 14 has been studied by X-ray diffraction. The
structure has been Solved from diffractometer data by Patterson method and
refined by blocked full-matrix least squares on the basis of 3082 observed
reflections to R and R(w) values of 0.0346 and 0.0381, respectively. The
structure shows the presence of two bridging hydrides between the niobium and
gold atoms; one of them is found close to the terminal hydride.
|
| S. E. Krami; Y. Mourad; D. Lucas; Y. Mugnier; A.
Antiñolo; M. Fajardo; S. García-Yuste; A. Otero
J. Organomet. Chem.
1996, 525, 125-131.
Electrochemical synthesis and reactivity of carbonato-niobocene complexes
The addition of the CO32- dianion to the electrogenerated species
Nb(eta(5)-C(5)H(5)RR')(2)Cl (2: R = H, R' = SiMe(3); 2': R = R' = SiMe(3))
gives in ca. 50% yields the anionic carbonate niobium(III) complex
[Nb(eta(5)-C(5)H(3)RR')(2)(O (C) over bar(O)O-O,O')](-) (3: R = H, R' =
SiMe(3); 3': R = R' = SiMe(3)) which are oxidized electrochemically to the
corresponding paramagnetic niobium(IV) complex [Nb(eta(5)- C(5)H(3)RR')(2)(OC(O)O-O,O')]
(5: R = H, R' = SiMe(3); 5': R = R' = SiMe(3)). These paramagnetic derivatives
have been characterized by ESR and IR spectroscopy. Mechanistic aspects
concerning the formation of 3 and 3' are discussed. 3 can also be obtained
from two-electron reduction of Nb(eta(5)-C(5)H(4)SiMe(3))(2)(O)Cl, 4, in the
presence of carbon dioxide. The addition of the formate anion HCO2- to 3 gives
the formato complex Nb(eta(5)-C(5)H(4)SiMe(3))(2)(OC(O)H-O,O') 6. |
| D. Lucas; Z. Modarres-Tehrani; Y. Mugnier; A. Antiñolo;
I. Del Hierro; A. Otero; M. Fajardo
New J. Chem. 1996, 20, 385-391.
New nitrile niobocene complexes; electrochemical studies
on their h1/h2 nitrile isomerization processes
The one-electron reduction of Nb(eta(5)- C(5)H(3)RR')(2)X(2) (1:R=SiMe(3),
R'=H, X=Cl; 1'; R=SiMe(3), R'=H, X=Br; 1 '': R=R'=SiMe(3), X=Cl) in the
presence of nitrile compounds R '' CN (a:R ''=CH3; b: R ''=Ph) initially
yields the corresponding eta(1)-nitrile- containing niobium(III)
complexes;Nb(eta(5)- C(5)H(3)RR')(2) X(eta(1)-R '' CN) (3a, 3'a, 3 '' a, and 3
'' b) identified by electrochemical methods. These species evolve at room
temperature to the more thermodynamically stable eta(2)-nitrile-containing
complexes, Nb(eta(5)-C(5)H(3)RR')(2)X(eta(2)-R '' CN) (5a, 5'a, 5 '' a and 5
'' b). complexes 5a and Nb(eta(5)- C(5)H(4)SiMe(3))(2)Cl(eta(-)Ph CN) 5b were
alternatively prepared and characterized from the chemical reaction of
Nb(eta(5)-C(5)H(4)SiMe(3))(2)Cl 2 with a and b, respectively. Kinetic studies
from electrochemical data have allowed us to establish the rate constant for
the 3a-->5a isomerization process at 7.31 x 10(-5) and 5.75 x 10(-4) s(-1) at
0 degrees C and 28 degrees C, respectively (activation energy: Delta E#=55.83:
kJmol(- 1)). Finally, a reverse isomerization process (eta(2)-- >eta(1)
nitrile) has been observed for the paramagnetic cationic niobium (IV)
complexes, [Nb(eta(5)- C(5)H(3)RR')(2)X(eta(2)-R '' CN)](+) 6 and [Nb(eta(5)-
C(5)H(3)RR')(2)X(eta(1)-R '' CN)](+) 4, generated from electrochemical
oxidation of the corresponding niobium (III) derivatives 5 and 3. |
| A. Antiñolo; F. Carrillo-Hermosilla; M. Fajardo; S.
García-Yuste; M. Lanfranchi; A. Otero; M. A. Pellinghelli; S. Prashar; E.
Villaseñor
Organometallics 1996, 15, 5507-5513.
Studies on the Insertion Reactions of Activated Alkynes
into Nb-H Bonds in Hydride-Niobocene Complexes. X-ray Crystal Structures of Nb(h5-C5H4SiMe3)2(H)[h2-RO2C(H)=C(H)CO2R](R=Me
or tBu)
The hydride isocyanide complexes, Nb(eta(5)- C(5)H(4)SiMe(3))(2)(H)(CNR), R=xylyl=2,6-dimethylphenyl;
Cy (cyclohexyl); (t)Bu; as well as the hydride carbonyl complex
Nb(eta(5)-C(5)H(4)SiMe(3))(2)(H)(CO) react with several activated alkynes to
afford the corresponding alkenyl isocyanide complexes Nb(eta(5)-
C(5)H(4)SiMe(3))(2)(CNR)(C(R')=CH(R '')), R=xylyl, R'=R ''=CO(2)Me 1; R=Xylyl,
R'=R ''=CO(2)(t)Bu 2; R=Xylyl, R'=CO(2)Me, R ''=H 3; R=Xylyl, R'=CO(2)Me, R
''=Me 4; R=Cy, R'=R ''=CO(2)Me 5; R=Cy, R'=R ''=CO(2)(t)Bu 6; R=Cy,
R'=CO(2)Me, R ''=Me 7; R=(t)Bu, R'=R ''=CO(2)Me 8; (t)Bu, R'=R ''=CO(2)(t)Bu 9
and alkenyl-carbonyl complexes, Nb(eta(5)-C(5)H(4)SiMe(3))(2)(CO)(C(R')=CH(R
'')), R'=R ''=CO(2)Me 10; R'=R ''=CO(2)(t)Bu 11; R'=CO(2)Me, R ''=H 12. The
reaction of hydride isocyanide complexes with activated alkynes gives cis-
insertion resulting in the formation of (E)-alkenyl products. However, the
hydride carbonyl derivative undergoes insertion to give, under kinetic
control, a mixture of (E)- and (Z)-alkenyl isomers. Finally, the trihydride
niobocene complex Nb(eta(5)- C(5)H(4)SiMe(3))(2)(H)(3), reacts with esters
RO(2)CC=CCO(2)R' or MeO(2)CC=CH to give the hydride olefin derivatives,
Nb(eta(5)- C(5)H(4)SiMe(3))(2)(H)[eta(2)-RO(2)C(H)=C(H)CO(2)R'], R=R'=Me 13;
R=R'=(t)Bu 14; and Nb(eta(5)- C(5)H(4)SiMe(3))(2)(H)[eta(2)-MeO(2)C(H)=CH2]
15, probably as the result of a stereospecific trans- insertion. The different
complexes have been characterized by spectroscopic methods. In addition, the
structure of 13 and 14 were determined by single crystal X-ray diffraction. |
| A. Antiñolo; I. Del
Hierro; M. Fajardo; S. García Yuste; A. Otero; O. Blacque; M. M. Kubicki; J.
Amaudrut
Organometallics 1996, 15, 1966-1971.
Chemistry of h2-CS2 Niobocene Complexes: Synthesis and
Characterization of New 1,3-dithiol-2-ylidene Complexes via Reactions with
Activated Alkynes
The reaction of CS2 with Cp'Nb-2(H)(eta(2)-CH2=CH2) or
Cp'Nb-2(H)(eta(2)-CH2-CHPh) (Cp' = eta(5)- C(5)H(4)SiMe(3)) affords the
alkylniobocene complexes Cp'Nb-2(Et)(eta(2)-CS2-C,S) (2) and Cp'Nb-
2(CH(2)CH(2)Ph)(eta(2)-CS2-C,S) (3), respectively. The interaction of
eta(2)-CS2-containing complexes Cp'2NbCl(eta(2)-CS2-C,S) with alkynes bearing
electron- withdrawing groups gives rise to a new family of 1,3-
dithiol-2-ylidene niobocene species, Cp'(2)NbX(=CS(R)C=C(R)S) (6, X = Cl, R =
CF3; 7, X = Cl, R = COOMe; 8, X = Cl, R = COO(t)Bu; 9, X = Et, R = COOMe; 10,
X = Et, R = COO(t)Bu; 11, X = CH(2)CH(2)Ph, R = COOMe; 12, X = CH(2)CH(2)Ph, R
= COO(t)Bu). In a similar way, with the carboxylate complexes Cp'Nb-2(OC(O)H-
O)(eta(2)-CS2-C,S) (4) and Cp'Nb-2(OC(O)CH3-O)(eta(2)- CS2-C,S) (5) as
starting materials, other 1,3-dithiol-2- ylidene species have been isolated
Cp'Nb-2(OC(O)Y- O)(=CS(R)C=C(R)S) (13, Y = H, R = COOMe; 14, Y = H, R =
COO(t)Bu; 15, Y = CH3, R = COOMe; 16, Y = CH3, R = COO(t)Bu). The structures
of all complexes have been determined by spectroscopic methods. The structure
of 2 was established by single-crystal diffractometry studies. The molecular
structure shows a typical bent- sandwich geometry around the niobium atom with
the ethyl and carbon disulfide ligands arrayed in the plane between the two
cyclopentadienyl rings. |
Colaboraciones científicas habituales
| University
of Sussex. Reino Unido. Prof. M.F.Lappert |
| Université
de la Bourgogne. Francia. Prof. Y.Mugnier |
| Université
Paul Sabatier. Toulouse. Francia. Prof. J.Escudie. |
| Universidad de Leipzig. Alemania. Prof. Evamarie Hey-Hawkins |
| Universidad
degli Studio di Parma. Italia. Prof. A.Tiripicchio |
| Instituto
Técnico Superior de Lisboa. Portugal.
Prof. M.R.Ribeiro
|
| Universidad
de Alcalá. España. Prof. C.López-Mardomingo |
| Universidad
Rey Juan Carlos. España. Prof.M.Fajardo |
| Universidad
de Barcelona. España. Prof. A.Lledó |
BECAS,AYUDAS Y PREMIOS RECIBIDOS
v
Becario del Instituto de
Asistencia y Promoción del Estudiante. Cursos 1974/78. Beca-Salario
v
Becario del Instituto de
Asistencia y Promoción del Estudiante. Cursos 1978/79.Beca para la realización
de Tesis doctoral.
v
Becario del Plan de Formación
de Personal Investigador. Becas en el Extranjero. Convocatoria 1983/84(BOE 16 de
Abril de 1983)
v
Premio Unión Fenosa de
Investigación en la Universidad de Castilla La Mancha.(Equipo Prof.A.Otero)
1996.
|
