Reactivity of a 1-Azavinylidene Ligand with Diphenylacetylene on a Ruthenium Carbonyl Cluster. A Remarkable Alkyne Insertion into a Metal−Nitrogen Bond

Cabeza, Javier A.; Rı́o, Ignacio del; Franco, R.; Grepioni, Fabrizia

doi:10.1021/om970259z

Cited by 25 publications

(24 citation statements)

References 15 publications

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“…A similar insertion of two PhCCH molecules into an RuÀN bond was recently reported for the triruthenium cluster [Ru 3 (m-H)(m-NCPh 2 )(CO) 10 ]. [20] Complex 1 reacted readily with an excess of HCCCOOMe under similar conditions to give yellow-orange crystals of 4 a-PF 6 . The IR bands at 2060 and 1699 cm À1 were assigned to terminal CO and methoxycarbonyl groups, respectively.…”

Section: Methodsmentioning

confidence: 99%

Unprecedented Formation of Five-, Six-, and Seven-Membered Metallacycles by Single and Double Insertion of Mono- and Disubstituted Alkynes into an Rh−O Bond

Yamamoto

Xiao-hong

2000

Angew. Chem. Int. Ed.

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Section: Methodsmentioning

confidence: 99%

Unprecedented Formation of Five-, Six-, and Seven-Membered Metallacycles by Single and Double Insertion of Mono- and Disubstituted Alkynes into an Rh−O Bond

Yamamoto

Xiao-hong

2000

Angew. Chem. Int. Ed.

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“…Interest in the synthesis and reactivity of late-transition-metal amido complexes has grown considerably in recent years as a consequence of the relative scarcity of such compounds and of their potential use in carbon±nitrogen bond-forming reactions (Cabeza et al, 1998). In this ®eld, we have recently communicated the ®rst insertion of a non-activated alkyne into a metal±nitrogen bond, achieved on a triruthenium cluster derived from benzophenone imine (Cabeza et al, 1997). In an extension of the interesting reactivity observed for these ruthenium complexes to other transition metals, we studied the reactivity of benzophenone imine with osmium (Cabeza et al, 2000) and rhenium carbonyl derivatives.…”

Section: Commentmentioning

confidence: 99%

Section: Data Collectionmentioning

confidence: 99%

(Benzophenone imine-N)nonacarbonyldirhenium(0)(Re—Re)

et al. 2001

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The reaction of [Re2(CO)10] with benzophenone imine in dichloroethane, in the presence of Me3NO, leads to the binuclear title compound, nonacarbonyl(diphenylmethanimine‐N)dirhenium(0)(Re—Re), [Re2(HN=CPh2)(CO)9]. Both Re atoms are in an octahedral environment. The HN=CPh2 ligand is attached to one of the metal atoms through the N atom, occupying an equatorial position. The equatorial carbonyl ligands of each octahedral fragment are staggered by 45°.

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“…A similar double insertion proceeded on treatment of 1 with 1-hexyne to give 3, but X-ray analysis revealed that the structure resulted from a head-to-tail double insertion. [20] Complex 1 reacted readily with an excess of HCCCOOMe under similar conditions to give yellow-orange crystals of 4 a-PF 6 . The olefinic proton in the Rh À CH moiety appeared as a doublet at d 5.69 in the 1 H NMR spectrum due to coupling with 103 Rh.…”

Section: Methodsmentioning

confidence: 99%

Unprecedented Formation of Five-, Six-, and Seven-Membered Metallacycles by Single and Double Insertion of Mono- and Disubstituted Alkynes into an Rh−O Bond

Yamamoto

Xiao-hong

2000

Angewandte Chemie

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Metal alkynyl complexes are currently of great interest [1,2] since they are valuable for constructing vinylidene or carbene complexes for use in organic synthesis. [3±8] Reactions of organotransition metal halides with 1-alkynes in the presence of anions such as PF 6 À , BF 4 À , and CF 3 SO 3 À are representative methods for the preparation of vinylidene complexes. [9] One ortho-methoxy group in (2,6-dimethoxyphenyl)diphenylphosphane (mdmpp) was demethylated in the reaction with the isoelectronic complexes [(h 6 -arene)RuCl 2 ] 2 (arene C 6 Me 6 , p-cymene, C 6 H 3 Me 3 ) and [Cp*MCl 2 ] 2 (M Rh, Ir) to give metal complexes with a (P,O)-chelating phosphane: [(h 6arene)RuCl(mdmpp-kP,kO)] [10,11] and [Cp*MCl(mdmpp-kP,kO)] [12,13] (Cp* C 5 Me 5 ). We recently reported the unprecedented insertion of tetracyanoethylene (tcne) and tetracyanoquinodimethane into the CÀH bond adjacent to the MÀO bonds of the above rhodium(iii) and iridium(iii) complexes to produce (Pin the case of tcne. [14] Treatment of the ruthenium(iii) complex with PhCCH in the presence of NaPF 6 in acetone/CH 2 Cl 2 afforded the vinylidene complex [(h 6 -arene)Ru(mdmpp-kP,kO)( C CHPh)]-PF 6 . [15] However, treatment of [Cp*RhCl(mdmpp-kP,kO)] (1) [12] with 1-alkynes such as HCCCOOMe, PhCCH, and nBuCCH, and the disubstituted alkyne C 2 (CO 2 Et) 2 in the presence of NaPF 6 or KPF 6 resulted in unusual reactions (Scheme 1). In the reaction with HCCCOOMe, extraction of CO from the ester group of one and insertion of another 1-alkyne molecule into the RhÀO s bond occurred to produce a seven-membered metallacycle, and reactions with HC CR led to the formation of complexes with five-and six-membered rings by double insertion of 1-alkynes into the RhÀO bond. The disubstituted alkyne also underwent single insertion into the RhÀO bond. Similar insertion of unsaturated molecules into the metal ± oxygen bonds of metal alkoxides was achieved with cyclooctadiene [16] and perfluoroolefins [17] such as F 2 CCF 2 and hexafluorocyclobutene. The insertion of alkynes into the transition metal to oxygen s bonds was achieved here for the first time. [18] Interestingly, these unprecedented reactions allow single and double insertion of alkynes into the RhÀO bond of 1 to be controlled by means of the alkyne substituents. Experimental SectionThe reactions were carried out with the same batch of catalyst in the absence of oxygen and water under the following conditions: (SiO) 2 TaÀH (prepared by impregnation, 18.8 Â 10 À6 mol of Ta, 1 equiv), alkane (40 Torr, 43 equiv), and H 2 (630 Torr, 710 equiv) were heated with an oil bath to the desired temperature (AE 1 8C) in a glass batch reactor (376 mL). During the reaction, aliquots were expended, brought to atmospheric pressure, and analyzed by gas chromatography (HP 5890 apparatus, Al 2 O 3 / KCl on fused silica column, 50m Â 0.32mm). Alkanes and H 2 were dried over freshly regenerated molecular sieves (3) and deoxo traps before addition.[1] For the low-temperature hydrogenolysis of alkanes on group IV silica supported comple...

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Reactivity of a 1-Azavinylidene Ligand with Diphenylacetylene on a Ruthenium Carbonyl Cluster. A Remarkable Alkyne Insertion into a Metal−Nitrogen Bond

Abstract: The insertion of diphenylcetylene into a ruthenium-nitrogen bond is a key step in the preparation of the binuclear derivative 2. This is the first example of insertion of a little electrophilic alkyne into a metalnitrogen bond.

Cited by 25 publications

References 15 publications

Unprecedented Formation of Five-, Six-, and Seven-Membered Metallacycles by Single and Double Insertion of Mono- and Disubstituted Alkynes into an Rh−O Bond

Unprecedented Formation of Five-, Six-, and Seven-Membered Metallacycles by Single and Double Insertion of Mono- and Disubstituted Alkynes into an Rh−O Bond

(Benzophenone imine-N)nonacarbonyldirhenium(0)(Re—Re)

Unprecedented Formation of Five-, Six-, and Seven-Membered Metallacycles by Single and Double Insertion of Mono- and Disubstituted Alkynes into an Rh−O Bond

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