Reversible exchange of (.eta.5-cyclopentadienyl)(dinitrosoalkane)cobalt complexes with alkenes. Kinetic and spectroscopic evidence for cyclopentadienyldinitrosylcobalt as a reactive intermediate

Becker, Paul; Bergman, Robert G.

doi:10.1021/ja00348a011

Cited by 49 publications

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“…Detailed mechanistic studies conducted by Bergman have subsequently revealed that the addition process proceeds through the intermediacy of CpCo(NO) 2 , which is generated by the reaction of NO with 291 . 206 …”

Section: Transition Metal-catalyzed Diaminationmentioning

confidence: 99%

Methods for direct alkene diamination, new & old

2012

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The 1,2-diamine moiety is a ubiquitous structural motif present in a wealth of natural products, including non-proteinogenic amino acids and numerous alkaloids, as well as in pharmaceutical agents, chiral ligands and organic reagents. The biological activity associated with many of these systems and their chemical utility in general has ensured that the development of methods for their preparation is of critical importance. While a wide range of strategies for the preparation of 1,2-diamines have been established, the diamination of alkenes offers a particularly direct and efficient means of accessing these systems. The purpose of this review is to provide an overview of all methods of direct alkene diamination, metal-mediated or otherwise.

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Section: Transition Metal-catalyzed Diaminationmentioning

confidence: 99%

Methods for direct alkene diamination, new & old

2012

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“…(1)]. 2, 5a–c More recently this chemistry has been used to develop a method for CC bond formation 5d,e. In addition, the reaction of K[IrCl 5 (NO)] with alkenes to yield iridium nitrosoalkane complexes,6 and the reaction of [TpRuCl 2 (NO)] (Tp=tris(pyrazolyl)borate) with 2‐vinylpyridine to yield a nitrosoalkene complex have been reported 7…”

Section: Methodsmentioning

confidence: 99%

Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

2011

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While the activation of relatively inert gases such as N 2 and CO with organometallic complexes remains a topic of intense investigation, methods for controlling the reactivity of nitric oxide at transition-metal centers have received considerably less attention. [1][2][3] For example, the migratory insertion of NO into metal-alkyl or metal-aryl bonds has been observed in only a handful of metal complexes, [3] despite the analogous reaction of CO dominating its organometallic chemistry and being the key step in many homogeneous catalytic processes. Although the paucity of studies in this field may be a reflection of the often complicated background reactivity of NO, [4] the potential to develop selective reactions incorporating NO that form new carbon-nitrogen bonds represents an attractive approach in organic synthesis.It is in this context that we are interested in the ligandbased reaction of metal nitrosyl complexes with alkenes.[5] In the absence of metal coordination the reaction chemistry of NO with alkenes is unruly.[4] Furthermore, only a few transition-metal complexes have been shown to promote this reaction selectively. Thus, inspired by an early finding of Brunner and Loskot, we demonstrated in the 1980s that [{CpCo(NO)} 2 ], NO and strained or alkyl-substituted alkenes react cleanly to form the corresponding dinitrosoalkane complexes [1, Eq. (1)].[2, 5a-c] More recently this chemistry has been used to develop a method for C À C bond formation. [5d,e] In addition, the reaction of K[IrCl 5 (NO)] with alkenes to yield iridium nitrosoalkane complexes, [6] and the reaction of [TpRuCl 2 (NO)] (Tp = tris(pyrazolyl)borate) with 2-vinylpyridine to yield a nitrosoalkene complex have been reported. [7] In spite of the above reactions, there are not many C À N bond-forming reactions of metal nitrosyls and double additions remain especially rare. We now report an example of this type of reactivity with the novel dinitrosyl complex [RuCl 2 (NO) 2 (THF)], which binds alkenes to the nitrosyl nitrogen atoms at room temperature in the presence of an additional neutral chelating ligand, L 2 . (2) as a brown crystalline solid in 88 % yield (Scheme 1). In the solid state, 2 possesses near-perfect square-based pyramidal geometry at the metal (t = 0.04), [8] with one bent NO ligand occupying the apical site and one linear NO ligand occupying an equatorial site trans to coordinated THF (Figure 1). The remaining trans-disposed coordination sites of the basal plane are occupied by chloride ligands.Complex 2 represents a rare example of a metal dinitrosyl complex possessing both linear and bent nitric oxide ligands in the solid state. The first structurally characterized example of such a complex, [RuCl(NO) 2 (PPh 3 ) 2 ]PF 6 (3), was reported by Eisenberg and co-workers and, while cationic, provides an important point of comparison. [9,10] The bending of apical nitrosyl ligands in five-coordinate complexes has been the topic of theoretical discussions.[11] Although ruthenium-nitrogen bond lengths (3, 1.743(20) ; 2, 1.727(5)...

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“…The ability of the olefin ligand to exchange for another olefin if activated thermally or photochemically was discovered by Becker and Bergman (1983a). They were able to obtain kinetic evidence for the formation of a discrete intermediate in these exchange reactions, postulating that [CpCo(NO)] 2 (40) would be the most plausible intermediate.…”

Section: Phosphitesmentioning

confidence: 99%

The broad diversity of CpCo(I) complexes

Thiel

Hapke

2014

Reviews in Inorganic Chemistry

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AbstractThe presented review will focus on the systematic overview of the available synthetic approaches and the reactivity and the structural characteristics of selected mononuclear CpCo(I) complexes with (non)chelating neutral donor ligands. The complexes containing symmetrical or unsymmetrical neutral ligand combinations aside from the anionic cyclopentadienyl (Cp) ligand will be discussed and the differences to complexes with substituted Cp ligands will be considered in selected cases.

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Reversible exchange of (.eta.5-cyclopentadienyl)(dinitrosoalkane)cobalt complexes with alkenes. Kinetic and spectroscopic evidence for cyclopentadienyldinitrosylcobalt as a reactive intermediate

Cited by 49 publications

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Methods for direct alkene diamination, new & old

Methods for direct alkene diamination, new & old

Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

The broad diversity of CpCo(I) complexes

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Reversible exchange of (.eta.5-cyclopentadienyl)(dinitrosoalkane)cobalt complexes with alkenes. Kinetic and spectroscopic evidence for cyclopentadienyldinitrosylcobalt as a reactive intermediate

Cited by 49 publications

References 0 publications

Methods for direct alkene diamination, new & old

Methods for direct alkene diamination, new & old

Synthesis of [RuCl2(NO)2(THF)] and its Double CN Bond‐Forming Reactions with Alkenes

The broad diversity of CpCo(I) complexes

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Synthesis of [RuCl₂(NO)₂(THF)] and its Double CN Bond‐Forming Reactions with Alkenes