Reactions between nitrosylpentaammineruthenium(II) and hydroxylamine or hydrazine. Formation of (dinitrogen oxide)pentaammineruthenium(II)

Bottomley, Frank; Crawford, Janice R.

doi:10.1021/ja00781a017

Cited by 51 publications

(17 citation statements)

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“…As described previously, 1 reacts with N 2 O and organic azides to liberate ethylene and dinitrogen, giving Cp* 2 Ti(O)py ( 20 ) and Cp* 2 TiNR ( 21 ), respectively (Scheme ). , By analogy to the oxygen- and nitrene-transfer reactions, carbene complex 22 (Scheme ) would be the expected product of the reaction of a diazoalkane with 1 . If N 2 O − and azide complexes , similar to 2 are formed on the reaction path to 20 and 21 , they lose nitrogen much more rapidly than does 2 . Complex 2 liberates dinitrogen slowly to generate what is presumed to be a carbene complex intermediate, which then reacts with a variety of substrates (vide infra).…”

Section: Discussionmentioning

confidence: 99%

Synthesis of an η²-N₂-Titanium Diazoalkane Complex with Both Imido- and Metal Carbene-Like Reactivity Patterns

et al. 1998

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The novel η 2 -N 2 -diazoalkane complex Cp* 2 Ti(N 2 CHSiMe 3 ) (2) has been prepared by addition of (trimethylsilyl)diazomethane to Cp* 2 Ti(C 2 H 4 ) (1). The structure of 2 reveals nearly symmetric Ti-N distances and an N-N distance ∼0.1 Å longer than that of the free diazoalkane. Compound 2 loses dinitrogen in solution under mild conditions to give the fulvene complex Cp*FvTiCH 2 SiMe 3 (4). Thermolysis of 2 in the presence of 1-alkenes yields the trans-R, -disubstituted titanacyclobutane complexes Cp* 2 Ti(CH(SiMe 3 )CH- (9)). The regio-and stereochemistry of the titanacyclobutane complexes was determined by a combination of one-and two-dimensional NMR techniques. The NMR assignment was supported in the case of 8 by an X-ray diffraction study. In addition to confirming the regio-and stereochemistry of the metallacycle, the X-ray structure of 8 shows that unlike most titanacyclobutanes, the metallacycle ring is puckered. A kinetic study of the formation of 7 from 2 and styrene revealed that the reaction is first order in 2 and zero order in styrene. The rate constant for this reaction is identical to that measured for the conversion of 2 to 4. The kinetic study supports a mechanism involving initial rate-determining loss of dinitrogen to form a carbene complex intermediate which undergoes hydrogen transfer from a Cp* methyl to give 4, or in the presence of styrene is trapped to form 7. In addition to its metal carbene-like reactions involving N 2 loss, complex 2 undergoes a variety of transformations in which N 2 is retained in the final product. These include cycloaddition reactions with alkynes and allene, as well as reversible reactions with Lewis bases to form adducts. These transformations, which are similar to reactions of group IV imido complexes, demonstrate the imide-like character of the diazoalkane ligand.

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Section: Discussionmentioning

confidence: 99%

Synthesis of an η²-N₂-Titanium Diazoalkane Complex with Both Imido- and Metal Carbene-Like Reactivity Patterns

et al. 1998

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“…Due to the thermodynamic oxidizing power of nitrous oxide (Δ G f 0 = 25 kcal/mol) and its kinetic inertness in the absence of a suitable activating metal center, the development of systems capable of catalyzing the oxidation of organic or inorganic substrates using this greenhouse feedstock represents a paradigm in inorganic chemistry. , Unlike most common powerful oxidants, nitrous oxide is cheap and very soluble in organic solvents such as toluene, alcohols, ethers, oils, water, and acids, with the advantage of such a chemical being resourceful, nonflammable, and essentially harmless. Therefore, it is not surprising that there has been considerable interest in employing N 2 O for oxygen-atom transfer reactions. − Unfortunately, and as noted before, this molecule is kinetically inert due to its poor properties as a ligand, − consequently resulting in only a handful of systems being capable of complexing N 2 O without the entropic and enthalpic driving force to N 2 ejection and metal oxo formation. ,,,− Thus, the use of N 2 O as an oxidizing substrate in transition metal chemistry is often hampered by a combination of kinetic inertness and inevitable oxidation of the metal center, concomitant with entropy-assisted loss of a thermodynamically stable molecule such as dinitrogen …”

Section: Introductionmentioning

confidence: 99%

Functionalization of Complexed N₂O in Bis(pentamethylcyclopentadienyl) Systems of Zirconium and Titanium

et al. 2014

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Methyl triflate reacts with the metastable azoxymetallacyclopentene complex Cp*2Zr(N(O)NCPhCPh), generated in situ from nitrous oxide insertion into the Zr–C bond of Cp*2Zr(η2-PhCCPh) at −78 °C, to afford the salt [Cp*2Zr(N(O)N(Me)CPhCPh)][O3SCF3] (1) in 48% isolated yield. A single-crystal X-ray structure of 1 features a planar azoxymetallacycle with methyl alkylation taking place only at the β-nitrogen position of the former Zr(N(O)NCPhCPh) scaffold. In addition to 1, the methoxy-triflato complex Cp*2Zr(OMe)(O3SCF3) (2) was also isolated from the reaction mixture in 26% yield and fully characterized, including its independent synthesis from the alkylation of Cp*2Zr=O(NC5H5) with MeO3SCF3. Complex 2 could also be observed, spectroscopically, from the thermolysis of 1 (80 °C, 2 days). In contrast to Cp*2Zr(N(O)NPhCCPh), the more stable titanium N2O-inserted analogue, Cp*2Ti(N(O)NCPhCPh), reacts with MeO3SCF3 to afford a 1:1 mixture of regioisomeric salts, [Cp*2Ti(N(O)N(Me)CPhCPh)][O3SCF3] (3) and [Cp*2Ti(N(OMe)NCPhCPh)][O3SCF3] (4), in a combined 65% isolated yield. Single-crystal X-ray diffraction studies of a cocrystal of 3 and 4 show a 1:1 mixture of azoxymetallacyle salts resulting from methyl alkylation at both the β-nitrogen and the β-oxygen of the former Ti(N(O)NCPhCPh ring. As opposed to alkylation reactions, the one-electron reduction of Cp*2Ti(N(O)NCPhCPh) with KC8, followed by encapsulation with the cryptand 2,2,2-Kryptofix, resulted in the isolation of the discrete radical anion [K(2,2,2-Kryptofix)][Cp*2Ti(N(O)NCPhCPh)] (5) in 68% yield. Complex 5 was studied by single-crystal X-ray diffraction, and its solution X-band EPR spectrum suggested a nonbonding σ-type wedge hybrid orbital on titanium, d(z2)/d(x2–y2), houses the unpaired electron, without perturbing the azoxymetallacycle core in Cp*2Ti(N(O)NCPhCPh). Theoretical studies of Ti and the Zr analogue are also presented and discussed.

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“…The reduction of metal-coordinated NO by a nucleophile/base such as azide, hydroxylamine or hydrazine has been studied with pentacyanonitrosylferrate (nitroprusside, [Fe(CN) 5 [101,102] also led to NO reduction chemistry with added hydrazine, but N 2 O was not formed and instead azide (Eq. 9) or dinitrogen (Eq.…”

Section: Chemical Reduction Of Metal-bound Nomentioning

confidence: 99%

“…Actually, only one reasonably well characterized N 2 O coordination complex is known up to this day, i.e. that reported and studied by Armor and Taube [173][174][175] [102,174,176,177,180]. Without any X-ray crystallographic data available, no definite N 2 O coordination geometry can be described.…”

Section: 31mentioning

confidence: 99%

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Nitrogen Monoxide and Nitrous Oxide Binding and Reduction

Lee¹,

Mondal²,

Karlin³

2006

Activation of Small Molecules

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Reactions between nitrosylpentaammineruthenium(II) and hydroxylamine or hydrazine. Formation of (dinitrogen oxide)pentaammineruthenium(II)

Cited by 51 publications

References 5 publications

Synthesis of an η²-N₂-Titanium Diazoalkane Complex with Both Imido- and Metal Carbene-Like Reactivity Patterns

Synthesis of an η²-N₂-Titanium Diazoalkane Complex with Both Imido- and Metal Carbene-Like Reactivity Patterns

Functionalization of Complexed N₂O in Bis(pentamethylcyclopentadienyl) Systems of Zirconium and Titanium

Nitrogen Monoxide and Nitrous Oxide Binding and Reduction

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Reactions between nitrosylpentaammineruthenium(II) and hydroxylamine or hydrazine. Formation of (dinitrogen oxide)pentaammineruthenium(II)

Cited by 51 publications

References 5 publications

Synthesis of an η2-N2-Titanium Diazoalkane Complex with Both Imido- and Metal Carbene-Like Reactivity Patterns

Synthesis of an η2-N2-Titanium Diazoalkane Complex with Both Imido- and Metal Carbene-Like Reactivity Patterns

Functionalization of Complexed N2O in Bis(pentamethylcyclopentadienyl) Systems of Zirconium and Titanium

Nitrogen Monoxide and Nitrous Oxide Binding and Reduction

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Synthesis of an η²-N₂-Titanium Diazoalkane Complex with Both Imido- and Metal Carbene-Like Reactivity Patterns

Synthesis of an η²-N₂-Titanium Diazoalkane Complex with Both Imido- and Metal Carbene-Like Reactivity Patterns

Functionalization of Complexed N₂O in Bis(pentamethylcyclopentadienyl) Systems of Zirconium and Titanium