Binuclear Oxidative Addition of Hydrogen in Diamidonaphthalene‐Bridged Diiridium Complexes

Jiménez, M. Victoria; Sola, Eduardo; López, José A.; Lahoz, Fernando J.; Oro, Luis A.

doi:10.1002/(sici)1521-3765(19980807)4:8<1398::aid-chem1398>3.0.co;2-#

Cited by 42 publications

(11 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

supporting

confidence: 73%

“…[3] Homoleptic systems are of particular interest since these species may function as ™naked∫ metal atom reagents and are therefore valuable precursors for the general exploration of low-valent transition metal chemistry. [4] Except for the first reported homoleptic polyarene transition metal complex [Ru(C 10 H 8 ) 2 ] 2 (C 10 H 8 naphthalene), [5] all previous examples contained only early (Groups 4 ± 6) transition metals. [4] However, the existence of this cationic ruthenium species suggested that related neutral and anionic polyarene complexes of later transition metals should also be accessible.…”

Section: Dedicated To Professor Klaus Jonasmentioning

confidence: 99%

“…The oxidation of these d 8 d 8 diiridium compounds, to species of d 6 d 8 or d 7 d 7 electronic configurations, gave dihydrogen-activating compounds. [5] Here we report that such an oxidation strategy also allows the transformation of nonreactive d 8 d 8 compounds into dinuclear CÀH activating species.The treatment of the diamidonaphthalene ((NH 2 )naphth)-bridged diiridium (iii) complex [Ir 2 (m-1,8-(NH) 2 naphth)-(m-H)H 3 (NCCH 3 )(PiPr 3 ) 2 ] (1) with two equivalents of an internal alkyne such as 2-butyne or diphenylacetylene afforded diiridium(i) derivatives of the formula [Ir 2 (m-1,8-(NH) 2 naphth)(h 2 -Z-RHCCHR) 2 (PiPr 3 ) 2 ] (R Me (2), Ph (3)) [Eq. (1)].…”

mentioning

confidence: 99%

“…[5] The oxidation of 2 and 3 by [FeCp 2 ](CF 3 SO 3 ) took place under conditions similar to those employed for the oxidation of related diiridium(i) derivatives to metal ± metal bonded diiridium(ii) species. [5] Instead of the expected diiridium(ii) oxidation products, the reactions afforded the hydride-bridged diiridium(iii) complexes 4 and 5 [Eq. (2)], after the oxidative addition of an alkene ligand CÀH bond.…”

mentioning

confidence: 99%

“…The hydride ligand of 5 displays a 1 H NMR signal in CD 2 Cl 2 , which consists of a doublet of doublets at d À 17.86 with J(H,P) coupling constants of 49.5 and 11.1 Hz. The large value of the former coupling constant indicates a bridging hydride trans to one PiPr 3 ligand, [5] which supports the proposed structure depicted in Equation (2). This proposal is also consistent with the presence in the 1 H NMR spectrum of a singlet at d 6.86, which corresponds to the vinylic hydrogen, and three singlets at d 1.03, 2.55, and 2.90, attributed to three nonequivalent acetonitrile ligands.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Alkene C−H Activations at Dinuclear Complexes Promoted by Oxidation

Jiménez

Sola

Caballero

et al. 2002

Angew. Chem. Int. Ed.

Self Cite

View full text Add to dashboard Cite

show abstract

supporting

confidence: 73%

Section: Dedicated To Professor Klaus Jonasmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

Alkene C−H Activations at Dinuclear Complexes Promoted by Oxidation

Jiménez

Sola

Caballero

et al. 2002

Angew. Chem. Int. Ed.

Self Cite

View full text Add to dashboard Cite

show abstract

Reactivity of Triosmium Carbonyl Clusters with 1,8-Diaminonaphthalene − Synthesis and Structural Characterization of Amido, Diamido, andC-Metalated Trinuclear Derivatives

Cabeza¹,

Nöth²,

Rosales-Hoz³

et al. 2000

Eur. J. Inorg. Chem.

View full text Add to dashboard Cite

The compounds [Os3(CO)12] and [Os3(μ‐H)2(CO)10] do not react with 1,8‐diaminonaphthalene (H2dan) under thermal conditions (110 °C, 30 min). However, [Os3(CO)10(MeCN)2] reacts with H2dan (THF, reflux temperature) to give two isomers of [Os3(μ‐H)(μ‐Hdan)(CO)9] (1 and 2). In toluene at reflux temperature, these reagents afford [Os3(μ‐dan)(CO)10] (3). Compound 2 can be converted into 3 under thermal conditions, but no interconversion between 1 and 2 has been observed. The three compounds have been characterized by X‐ray diffraction methods. Compound 1 arises from the C‐metalation of H2dan in a position adjacent to an NH2 group; this generates a hydride and a ligand that interacts with the three metal atoms through one of the NH2 groups, through the metalated carbon atom (which spans an Os−Os edge), and through one of the C=C bonds of the metalated ring. In compound 2, the hydride arises from the oxidative addition of an N−H bond of H2dan; the resulting ligand interacts with two of the three metal atoms through the amido NH fragment (bridging position) and through the remaining NH2 group. Compound 3 is derived from the transformation of both NH2 groups of H2dan into amido NH groups and consists of a 50‐electron trinuclear cluster with the longest edge doubly‐bridged by both amido groups.

show abstract

Alkene C−H Activations at Dinuclear Complexes Promoted by Oxidation

et al. 2002

Self Cite

View full text Add to dashboard Cite

Several recent discoveries in the chemistry of transition metal di-and polynuclear complexes have disclosed new methods of hydrocarbon activation and functionalization, favored by polynuclear environments. [1,2] In parallel, considerable progress has been made in understanding the reactivity features resulting from multimetallic reaction sites. [1, 3,4] Together, such advances may contribute to the rational design of new catalysts and applications based on this type of compound. However, the proximity of the metal centers is likely to have significant repercussions for the reactivity, which remain to be determined.In our recent studies on ™open-book∫ d 8 diiridium complexes with N-donor bridges, we have observed a remarkable substrate selectivity in the reactions of these compounds towards oxidative addition reactants. Whereas the d 8 diiridium complexes underwent fast S N 2 oxidative additions with substrates such as halocarbons, [4] the additions of less-polar reactants such as dihydrogen were not observed. The oxidation of these d 8 d 8 diiridium compounds, to species of d 6 d 8 or d 7 d 7 electronic configurations, gave dihydrogen-activating compounds. [5] Here we report that such an oxidation strategy also allows the transformation of nonreactive d 8 d 8 compounds into dinuclear CÀH activating species.The treatment of the diamidonaphthalene ((NH 2 )naphth)bridged diiridium (iii) complex [Ir 2 (m-1,8-(NH) 2 naphth)-(m-H)H 3 (NCCH 3 )(PiPr 3 ) 2 ] (1) with two equivalents of an internal alkyne such as 2-butyne or diphenylacetylene afforded diiridium(i) derivatives of the formula [Ir 2 (m-1,8-(NH) 2 naphth)(h 2 -Z-RHCCHR) 2 (PiPr 3 ) 2 ] (R Me (2), Ph (3)) [Eq. (1)]. The solution NMR spectra of both compounds indicate symmetric C 2 structures with a transoid arrangement of nonrotating Z-alkene ligands. These features have been confirmed by the X-ray crystallographic determination of the structure of 2, [6] (Figure 1). reaction see: M. AlajarÌn, C. Conesa, H. S. Rzepa, J. Chem. Soc.

show abstract

Binuclear Oxidative Addition of Hydrogen in Diamidonaphthalene‐Bridged Diiridium Complexes

Cited by 42 publications

References 61 publications

Alkene C−H Activations at Dinuclear Complexes Promoted by Oxidation

Alkene C−H Activations at Dinuclear Complexes Promoted by Oxidation

Reactivity of Triosmium Carbonyl Clusters with 1,8-Diaminonaphthalene − Synthesis and Structural Characterization of Amido, Diamido, andC-Metalated Trinuclear Derivatives

Alkene C−H Activations at Dinuclear Complexes Promoted by Oxidation

Contact Info

Product

Resources

About