Two-step radical reactions that switch low multiplicity channels leading to the carbene and carbyne species detected for Ru(5F) + CH4−nFn (n = 2–4) interactions under matrix isolation conditions

Torres, Ana E.; Méndez, Óscar; Colmenares, Fernando

doi:10.1039/c3ra41316k

Cited by 10 publications

(10 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Previously, we proposed a non‐spin flip reaction scheme that allowed explaining the low‐spin carbene and carbyne complexes determined under matrix‐isolation conditions for the interactions of fluoromethanes with laser‐ablated ruthenium atoms . According to this model, the observed products for these interactions emerge from two sequential reactions.…”

Section: Introductionmentioning

confidence: 99%

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH₃CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

2017

Self Cite

View full text Add to dashboard Cite

Results emerging from a CASSCF‐MRMP2 study are used to explain the products observed under matrix isolation conditions for the interactions M + CH3CN (M=V(4F), Nb(6D), Ta(4F)). A two‐reaction scheme is proposed to rationalize the low‐spin inserted species detected for the niobium and tantalum interactions, mainly the quadruplet CH3‐Nb‐NC and the doublet CH2=Ta‐(H)NC compounds, respectively. According to this scheme, the radicals CH3 + M‐NC are formed in each case from the ground state of the reactants. As these radical fragments remain trapped in the matrix they can recombine themselves in a second reaction, which evolves to the low‐spin observed products. The absence of inserted products for the vanadium reaction is also explained in terms of this scheme. The picture attained for the investigated reactions fits better with the available experimental data than previous descriptions based on spin‐flip models.

show abstract

Section: Introductionmentioning

confidence: 99%

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH₃CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…A similar two-step radical reaction scheme has been used in previous contributions to explain for the observed products in other reactions. [33][34][35][36][37][38] Although mass-spectrometry determinations on these reactions have inspired the present study, this investigation is mainly focused on the analysis of the factors that could be relevant in determining the role of the metal-ligand interactions on the NH 3 activation by the ammine complexes yielded by sequential addition of NH 3 ligands to the metallic center. However, even when our reaction models do not consider the experimental conditions of the spectroscopic determinations, there is a good agreement between the results presented herein and those obtained by mass spectrometry for the investigated interactions.…”

mentioning

confidence: 99%

Low‐Energy Pathways Found for the NH₃ Activation and H₂ Elimination by the Werner‐Type Complexes M(NH₃)₄⁺ (M=Fe, Ru and Os).

2020

Self Cite

View full text Add to dashboard Cite

The interactions of NH3 with the transition metal complexes M(NH3)n+ (M=Fe, Ru, Os; n=0−4) were investigated theoretically with the aim of analyzing the factors that determine their reactivity patterns and product distributions. The reactions of ammonia with the low‐coordination complexes of the three metallic ions (n=1−3) lead only to the addition product M(NH3)n+1+. However, once the highest‐coordinated complex M(NH3)4+ is reached, each of the reactions evolves to metal‐inserted species through low energy channels. For osmium, the hydrogen abstraction from an additional NH3 molecule by the inserted intermediate H−Os(NH3)4‐NH2+ leads to H2 elimination products along a favorable pathway. The facile breaking of the strong N−H bond of ammonia by these Werner‐type complexes is by far the most striking finding emerging from this study. Hopefully, this could inspire future contributions in the areas of chemical and bioinorganic catalysis.

show abstract

“…e low-spin carbenes and carbynes detected in the IR-matrix spectra for the reactions of zirconium, iron, and ruthenium with fluoromethanes were rationalized by means of two sequential radical reactions [26][27][28]. Likewise, in a recent contribution, we have extended the use of this scheme to the description of interactions involving transition-metal complexes.…”

Section: Spin-flip Models Versus the Two-step Reaction Schemementioning

confidence: 91%

Applying a Nonspin-Flip Reaction Scheme to Explain for the Doublet Sulfide Oxides SMO₂ Observed for the Reactions of SO₂ with V(⁴F), Nb(⁶D), and Ta(⁴F)

Velásquez

Torres

Seminario

et al. 2018

Journal of Nanotechnology

Self Cite

View full text Add to dashboard Cite

Energy profiles linking the reactants M + SO2 (M = V(4F), Nb(6D;4F), and Ta(4F)) with the products observed for these reactions under matrix-isolation conditions, mainly the oxide complex OV(η2-SO) and the sulfide oxides SVO2, SNbO2, and STaO2, have been obtained from DFT and CASSCF-MRMP2 calculations. For each of these interactions, the radical fragments MO + SO can be reached from the lowest-lying quadruplet electronic states of the reactants. As the quadruplet and doublet radical asymptotes that vary only in the spin of the unpaired parallel electrons of the nonmetallic fragment are degenerated, a second reaction leading to the rebounding of the radical fragments can take place through both multiplicity channels. Reaction along the doublet pathway leads in each case to the most stable structure for the oxide SMO2. For the vanadium interaction, recombination of the radical species through the quadruplet channel explains for the oxide product OV(η2-SO).

show abstract

Two-step radical reactions that switch low multiplicity channels leading to the carbene and carbyne species detected for Ru(5F) + CH4−nFn (n = 2–4) interactions under matrix isolation conditions

Cited by 10 publications

References 42 publications

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH₃CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH₃CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

Low‐Energy Pathways Found for the NH₃ Activation and H₂ Elimination by the Werner‐Type Complexes M(NH₃)₄⁺ (M=Fe, Ru and Os).

Applying a Nonspin-Flip Reaction Scheme to Explain for the Doublet Sulfide Oxides SMO₂ Observed for the Reactions of SO₂ with V(⁴F), Nb(⁶D), and Ta(⁴F)

Contact Info

Product

Resources

About

Two-step radical reactions that switch low multiplicity channels leading to the carbene and carbyne species detected for Ru(5F) + CH4−nFn (n = 2–4) interactions under matrix isolation conditions

Cited by 10 publications

References 42 publications

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH3CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH3CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

Low‐Energy Pathways Found for the NH3 Activation and H2 Elimination by the Werner‐Type Complexes M(NH3)4+ (M=Fe, Ru and Os).

Applying a Nonspin-Flip Reaction Scheme to Explain for the Doublet Sulfide Oxides SMO2 Observed for the Reactions of SO2 with V(4F), Nb(6D), and Ta(4F)

Contact Info

Product

Resources

About

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH₃CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

Rationalizing the Low‐Spin Products Observed for the Reactions M+CH₃CN (M=V, Nb,Ta) Through a Non‐Spin Flip Scheme.

Low‐Energy Pathways Found for the NH₃ Activation and H₂ Elimination by the Werner‐Type Complexes M(NH₃)₄⁺ (M=Fe, Ru and Os).

Applying a Nonspin-Flip Reaction Scheme to Explain for the Doublet Sulfide Oxides SMO₂ Observed for the Reactions of SO₂ with V(⁴F), Nb(⁶D), and Ta(⁴F)