Reaction of nitrogen oxides with π-allyl complexes: A model for propylene oxidation

Clément, Roxanne; Klabunde, U.; Parshall, G. W.

doi:10.1016/0304-5102(78)80001-7

Cited by 15 publications

(4 citation statements)

References 12 publications

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“…Moreover, the addition of NO to [NiBr(C 3 H 5 ) 2 ] 2 results in the formation of 3-oximinopropene. 17 While the mechanism of this transformation was not fully elucidated, it was proposed to proceed through a Ni−NO intermediate. Finally, Warren and coworkers reported that the addition of ArNO (Ar = 3,5-Me 2 C 6 H 3 ) to [Ar 2 nacnac]NiNO (Ar 2 nacnac = ArNC(Me)-CHC(Me)N Ar; Ar = 2,6-i Pr 2 C 6 H 3 ) gives [Ar 2 nacnac]Ni(κ 2 -ONN(Ar)O) as the isolated product.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In contrast to the chemistry reported for groups 8 and 9, the reactivity of group 10 metal nitrosyls with nucleophiles has not been well explored, in part because of the relative rarity of these complexes. , However, there are a handful of reports that detail the reactivity of nickel nitrosyls with nucleophiles. − For instance, CpNiNO reacts with RLi (R = Ph, t Bu) to form a trinuclear bridging imido complex, [Cp 3 Ni 3 (μ 3 -NR)], as the isolated product . This reaction is thought to proceed via nucleophilic attack at the N atom of the NO ligand.…”

Section: Introductionmentioning

confidence: 99%

“…This reaction is thought to proceed via nucleophilic attack at the N atom of the NO ligand. Moreover, the addition of NO to [NiBr(C 3 H 5 ) 2 ] 2 results in the formation of 3-oximinopropene . While the mechanism of this transformation was not fully elucidated, it was proposed to proceed through a Ni–NO intermediate.…”

Section: Introductionmentioning

confidence: 99%

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Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]

Wright

Hayton

2011

Inorg. Chem.

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The reaction of [NO][PF(6)] with excess Ni powder in CH(3)NO(2), in the presence of 2 mol % NiI(2), results in the formation of [Ni(NO)(CH(3)NO(2))(3)][PF(6)] (1), which can be isolated in modest yield as a blue crystalline solid. Also formed in the reaction is [Ni(CH(3)NO(2))(6)][PF(6)](2) (2), which can be isolated in comparable yield as a pale-green solid. In the solid state, 1 exhibits tetrahedral geometry about the Ni center with a linear nitrosyl ligand [Ni1-N1-O1 = 174.1(8)°] and a short Ni-N bond distance [1.626(6) Å]. As anticipated, the weakly coordinating nitromethane ligands in 1 are easily displaced by a variety of donors, including Et(2)O, MeCN, and piperidine (NC(5)H(11)). More surprisingly, the addition of mesitylene to 1 results in the formation of an η(6)-coordinated nickel arene complex, [Ni(η(6)-1,3,5-Me(3)C(6)H(3))(NO)][PF(6)] (6). In the solid state, complex 6 exhibits a long Ni-C(cent) distance [1.682(2) Å], suggesting a relatively weak Ni-arene interaction, a consequence of the strong π-back-donation to the nitrosyl ligand. The addition of anisole to 1 also results in the formation of a η(6) nickel arene complex, [Ni(η(6)-MeOC(6)H(5))(NO)][PF(6)] (7). This complex also exhibits a long Ni-C(cent) distance [1.684(1) Å].

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]

Wright

Hayton

2011

Inorg. Chem.

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“…The connectivity of 4 l was determined unambiguously following a single‐crystal X‐ray diffraction experiment; however, the poor resolution of the data limits any informative discussion (see the Supporting Information, Figure S2). It is noteworthy that while analogous tautomerization products have not been observed in the alkene/[CpCo(NO) 2 ] reaction,2 a similar tautomerization has been observed in the insertion reaction of [NO][PF 6 ] with [CpCr(NO) 2 Me] to yield [CpCr(NO) 2 {N(OH)CH 2 }][PF 6 ],14 and upon reaction of [{(η 3 ‐allyl)NiBr} 2 ] with NO to form [NiBr(NO)(CH 2 CHCHNOH)] 3a…”

Section: Methodsmentioning

confidence: 65%

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 Coordination Chemistry of Pyrazole‐Derived Ligands

Trofimenko¹

1986

Progress in Inorganic Chemistry

658

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Reaction of nitrogen oxides with π-allyl complexes: A model for propylene oxidation

Cited by 15 publications

References 12 publications

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]

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

The Coordination Chemistry of Pyrazole‐Derived Ligands

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Reaction of nitrogen oxides with π-allyl complexes: A model for propylene oxidation

Cited by 15 publications

References 12 publications

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO2)3][PF6]

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO2)3][PF6]

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

The Coordination Chemistry of Pyrazole‐Derived Ligands

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Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]

Late-Metal Nitrosyl Cations: Synthesis and Reactivity of [Ni(NO)(MeNO₂)₃][PF₆]

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