Miguel A. Ciriano

Instituto de Síntesis Química y Catálisis Homogénea

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Cristina Tejel

Universidad de Zaragoza

174

Luis A. Oro

Universidad de Zaragoza

161

José A. López

Universidad de Zaragoza

Fernando J. Lahoz

Instituto de Síntesis Química y Catálisis Homogénea

M. Pilar del Rı́o

Instituto de Síntesis Química y Catálisis Homogénea

Jesús J. Pérez‐Torrente

Instituto de Síntesis Química y Catálisis Homogénea

Bas de Bruin

University of Amsterdam

C. Tejel

Miguel A. Casado

Instituto de Síntesis Química y Catálisis Homogénea

António Tiripicchio

University of Parma

Cooperative Institutions

Universidad de Zaragoza

Consejo Superior de Investigaciones Científicas

Instituto de Síntesis Química y Catálisis Homogénea

Centre National de la Recherche Scientifique

Instituto de Nanociencia y Materiales de Aragón

University of Bristol

University of Amsterdam

University of Parma

Universidad de Alcalá

University of Cambridge

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2-Pyridonate (Opy) rhodium(I) carbonyl complexes. Crystal structure of the unusual tetranuclear complex [Rh₄(µ-Opy)₄(µ-CO)₂(CO)₄]

Journal of the Chemical Society. Dalton transactions (1987)

Miguel A. Ciriano B. Eva Villarroya Luis A. Oro María C. Apreda Concepción Foces‐Foces

Reaction of [Rh2(µ-Cl)2(CO)4] with 2-hydroxypyridine (HOpy) and potassium hydroxide in methanol yields the tetranuclear complex [Rh4(µ-Opy)4(µ-CO)2(CO)4](1), but the binuclear compound [Rh2(µ-Opy)2(CO)4](2) is obtained when the reaction is performed under one atmosphere of carbon monoxide. Both complexes interconvert: by addition of trimethylamine oxide [(2)→(1)], or bubbling of carbon monoxide [(1)→(2)]. The related complex [Rh2(µ-Opy)(µ-dppm)2(CO)2][ClO4](3)[dppm = bis(diphenylphosphino)methane] can be prepared by reaction of (2) with dppm and perchloric acid. Crystals of (1) are monoclinic, space group P21/n, with a= 19.429 3(9), b= 8.782 7(2), c= 8.439 9(2)Å, β= 98.912(3)°, and Z= 2. The structure was solved by Patterson and Fourier methods and refined by least-squares calculations to R= 0.058. The structure of the tetranuclear complex consists of two binuclear units, centrosymmetrically related, and joined together through 2-pyridonate groups. In each binuclear moiety a 2-pyridonate group and a carbonyl ligand bridge the two rhodium atoms, which are directly bonded [Rh–Rh 2.619 7(8)Å].

Monoclinic crystal system

Moiety

10.1039/dt9870000981

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Citations (15)

Diiridium(II)‐Komplexe durch lichtunterstützte oxidative Additionsreaktionen: Struktur eines stabilen zweikernigen Iodo(iodmethyl)iridium(II)‐Komplexes

Angewandte Chemie (1987)

Miguel A. Ciriano Fernando Viguri Luis A. Oro António Tiripicchio M. TIRIPICCHIO‐CAMELLINI

Keine Zwischenstufen zu alkylidenverbrückten Komplexen, sondern stabile Verbindungen sind die Diiridium(II)‐Komplexe 1 (X  CH 3 , CH 2 I). Die starke Beschleunigung der Synthese 1 → 2 durch Licht legt zwar einen Radikalmechanismus nahe, doch steht die Bildung eines Gemisches aus Chloro‐, Bromo‐ und Iodo‐Komplex bei der Synthese mit CH 2 I 2 in Gegenwart von [Bu 4 N]Br und CH 2 Cl 2 dazu in Widerspruch.

10.1002/ange.19870990508

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Citations (9)

Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM₂ (M = Rh, Ir) Early−Late Heterobimetallic Complexes

Organometallics (2003)

M.A.F. Hernandez-Gruel Jesús J. Pérez‐Torrente Miguel A. Ciriano Angel B. Rivas Fernando J. Lahoz

Reactions of the zirconium−sulfide metallocene anion [Cptt2ZrS2]2- (Cptt = η5-1,3-di-tert-butylcyclopentadienyl) with [{M(μ-Cl)(diolefin)}2 gave the d0−d8 complexes [Cptt2Zr(μ3-S)2{M(diolefin)}2] (M = Rh, diolefin = 2,5-norbornadiene (nbd) (1), 1,5-cyclooctadiene (cod); M = Ir, diolefin = cod) with a triangular ZrM2 core capped by two symmetrical μ3-sulfido ligands. The rhodium complexes [Cptt2Zr(μ3-S)2{Rh(diolefin)}2] (diolefin = tetrafluorobenzobarrelene (tfbb), nbd, cod) can also be prepared by the additive-deprotonation reactions of the mononuclear [Rh(acac)(diolefin)] (diolefin = nbd, tfbb) and the dinuclear [{Rh(μ-OH)(cod)}2] complexes with [Cptt2Zr(SH)2]. These compounds exist as two rotamers in solution due to a hindered rotation of the cyclopentadienyl rings and the relative disposition of the substituents of the Cptt groups in the sandwich moiety. The reaction of [Cptt2Zr(SH)2] with [Ir(acac)(cod)] gave the complex [Cptt(acac)Zr(μ3-S)2{Ir(cod)}2] (5) with release of HCptt and coordination of acetylacetonate to the zirconium center. Carbonylation of compounds 1 and 5 yielded [Cptt2Zr(μ3-S)2{Rh(CO)2}2] (6) and [Cptt(acac)Zr(μ3-S)2{Ir(CO)2}2], respectively, while the complexes [Cptt2Zr(μ3-S)2{M(CO)2}2] (M = Rh, Ir) resulted also from the reaction of [Cptt2Zr(SH)2] with (PPh3Bz)[MCl2(CO)2] in the presence of triethylamine. Reactions of the carbonyl complexes with 1 molar equiv of bis(diphenylphosphino)methane (dppm) gave the cisoid complexes [Cptt2Zr(μ3-S)2{M(CO)}2(μ-dppm)] (M = Rh (9), Ir) with evolution of carbon monoxide. Monodentate phosphites, P(OMe)3 and P(OPh)3, react with 6 to give mixtures of the transoid and cisoid isomers [Cptt2Zr(μ3-S)2{Rh(CO)(P(OR)3)}2], which also exhibit a restricted rotation of the Cptt rings. The molecular structures of complexes 6 and 9 have been determined by X-ray diffraction methods. Compound 6 in the presence of P-donor ligands, P(OMe)3, P(OPh)3, and PPh3, is a precursor of the catalyst for the hydroformylation of oct-1-ene under mild conditions of pressure and temperature. No Zr−Rh synergic effect is observed in this case, and the precursor breaks down after catalysis.

Triethylamine

Cyclopentadienyl complex

Carbonylation

Reactivity

Moiety

1,5-Cyclooctadiene

10.1021/om0209576

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Citations (40)

Pyrazolate thiocarbonylrhodium complexes. X-ray structure of [Rh(μ-3,5-Me2Pz)(CS)(PPh3)]2

Journal of Organometallic Chemistry (1982)

Rafael Usón Luis A. Oro Miguel A. Ciriano Daniel Carmona António Tiripicchio

Monoclinic crystal system

Dihedral angle

10.1016/s0022-328x(00)82568-1

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Citations (39)

Crescent-Shaped Rhodium(I) Complexes with Bis(o-carboxymethylphenyl)triazenide

Inorganic Chemistry (2004)

Cristina Tejel Miguel A. Ciriano G. Rios-Moreno Isabel T. Dobrinovitch Fernando J. Lahoz

Reaction of [[Rh(mu-Cl)(CO)2]2] with the triazene ArNNNHAr (Ar = o-CO2MeC6H4) produced the mononuclear complex [RhCl(ArNNNHAr)(CO)2] (1). Complex 1 reacted with KOH in methanol to give the dinuclear compound [[Rh(mu-ArNNNAr)(CO)2]2] (2), which showed a "mu-(1kappaN1,2kappaN3)-ArNNNAr" coordination mode for both bridging ligands. The dinuclear complex [[Rh(mu-ArNNNAr)(CO)2]2] (2) easily undergoes redistribution reactions in which the eight-membered "Rh2(NNN)2" core is broken. Thus, reaction of 2 with the anionic complex (NHEt3)[RhCl2(CO)2] gave the single-bridged complex (NHEt3)[Rh2(mu-ArNNNAr)Cl2(CO)4] (4), while the trinuclear complexes [Rh3(mu-ArNNNAr)(mu-Cl)(mu-CO)Cl(CO)4] (5) and [Rh3(mu-ArNNNAr)2(mu-Cl)(mu-CO)(CO)3] (6) were isolated by addition of the neutral compound [[Rh(mu-Cl)(CO)2]2] to 2, depending on the molar ratio employed. The formation of 5 and 6 involved the loss of carbonyl groups and the coordination of the oxygen atoms of the CO2Me groups. The structures of 4, 5, and 6 have been determined by X-ray diffraction methods, which show the ability of bis(o-carboxymethylphenyl)triazenide to act as bi-, tri-, and tetra-dentate ligand-spanning dinuclear moieties in trinuclear complexes.

Triazene

Bridging ligand

10.1021/ic049691g

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Citations (31)

NewEarly Zirconium-Sulfido Metallaligands forLate Transition Metals; Synthesis and Reactivity of [Cptt2Zr(SH)2] and [Cptt2Zr(SH)(OTf)]

European Journal of Inorganic Chemistry (1999)

M.A.F. Hernandez-Gruel Jesús J. Pérez‐Torrente Miguel A. Ciriano José A. López Fernando J. Lahoz

Reactivity

10.1002/(sici)1099-0682(199911)1999:11<2047::aid-ejic2047>3.0.co;2-r

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Citations (21)

CCDC 116623: Experimental Crystal Structure Determination

The Cambridge Structural Database (2000)

M.A.F. Hernandez-Gruel Jesús J. Pérez‐Torrente Miguel A. Ciriano Fernando J. Lahoz L.A. Oro

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

10.5517/cc3xc1d

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Citations (0)

CCDC 1014724: Experimental Crystal Structure Determination

The Cambridge Structural Database (2014)

Ana M. Geer Ángel L. Serrano Bas de Bruin Miguel A. Ciriano Cristina Tejel

10.5517/cc131x13

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Citations (0)

CCDC 139640: Experimental Crystal Structure Determination

The Cambridge Structural Database (2000)

C. Tejel Milena Sommovigo Miguel A. Ciriano Jörge A. López Fernando J. Lahoz

10.5517/cc4p9jm

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Reactions of bis(ethylene)(tertiary phosphine)platinum complexes with phenylethynyl derivatives of titanium and silicon; crystal structure of (µ-dimethylsilanediyl)(σ-phenylethynyl)[µ-(1-σ:1–2-η-phenylethynyl)]-bis(tricyclohexylphosphine)diplatinum (Pt–Pt)

Journal of the Chemical Society. Dalton transactions (1979)

Miguel A. Ciriano Judith A. K. Howard John L. Spencer F. G. A. Stone Hubert Wadepohl

Bis(ethylene)(tertiary phosphine)platinum complexes [Pt(C2H4)2(PR3)][PR3= P(cyclo-C6H11)3, PMe2Ph, PMePh2, PPh3, or PPri2Ph] react with bis(cyclopentadienyl)bis(phenylethynyl)titanium to give compounds [Pt{η-(PhCC)2Ti(η-C5H5)2}(PR3)] in which the PhCC–Ti–CCPh group acts as a bidentate ligand to platinum. In contrast, dimethylbis(phenylethynyl)silane reacts with [Pt(C2H4)2(PR3)][PR3= P(C6H11)3, PMeBut2, or PPri2Ph] to give diplatinum complexes [Pt2(σ-CCPh){µ-(1-σ:1–2-η-CCPh)}(µ-SiMe2)(PR3)2]. A single-crystal X-ray diffraction study has established the structure of the product from [Pt(C2,H4)2{P(C6H11)3}] and [Si(CCPh)2Me2]. Crystals are monoclinic, space group P21/c(no. 14), with a= 12.44(1), b= 26.12(4), c= 15.832(8)Å, β= 97.99(6)°, and Z= 4. The structure has been determined by analysis of 5 131 unique data with F > 4σ(F) collected to 2θ⩽ 50°(Mo-Kα radiation) at 200 K on a four-circle diffractometer, and refined to R 0.053 (R′0.041). The results establish a molecular structure with an SiMe2 group asymmetrically bridging a Pt–Pt separation of 2.703(1)Å. Two CCPh groups are σ-bonded to one metal atom (formally PtIV) but one is also η2-co-ordinated to the other platinum (formally PtII). The P–Pt–Pt–P skeleton is non-linear with PPtPt angles of 165.2(1) and 148.0(1)°. Dimethylbis(phenylethynyl)silane reacts with [Pt(C2H4)(PPh3)2], without carbon–silicon bond cleavage, to give mono- and di-platinum η2 complexes [Pt{η-PhCCSi(C2Ph)Me2}(PPh3)2] and [Pt2{η-(PhCC)2SiMe2}(PPh3)4].

Cyclopentadienyl complex

Monoclinic crystal system

Metallacycle

10.1039/dt9790001749

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Citations (67)