Hola Juan C y Diana K. Saludos.

Adjunto algunos artículos de referencia (señalados en

rojo). La química de NbCl5 es vasta…

Posibles mecanismos

I. En los primeros tiempos de reacción se observa una banda en el FTIR de la coordinación

entre el NbCl5 y la amina (1. Nb-NHC adducts DRX). De hecho, es necesario un exceso de
amina para que la reacción proceda. Eso es lo único que hemos visto, habría que estar
seguros.

De: 5. NbCl5 -tertiary amines: Ammonium salts have been isolated in a number of cases as
a result of the in situ production of HCl. The first structurally-characterized Nb(V) chloride
amido complex has been accessed by the straightforward 1:1 M reaction of NbCl5 with
NHEt2. Evidence has been collected for the occurrence of electron interchange in the
reactions of NbCl5 with trialkylamines, resulting in reduction of the metal centre and
amine C–H bond activation.

II. La coordinación con el grupo carboxilo con el átomo de Nb cambia la coordinación a

octaédrica. Esta coordinación en NbCl5 e Isopropoxido de Titanio permite rendimientos
cuantitativos. (En 2. Coord COO NbCl5 TiIOPr está la explicación de estos resultados)

De: 4. Review NbCl5 reactions: The chemistry of niobium and tantalum pentahalides,
MX5, with oxygen compounds has been elucidated in the very last years. Different types of
coordination adducts (neutral or ionic) can be isolated upon reaction of controlled
amounts of oxygen donors with MX5. The formation of coordination compounds may be the
first step of successive activation reaction involving the organic substrate, sometimes
unusual in the context of transition metal derivatives. The progress in the knowledge of the
direct interaction of MX5 with oxygen compounds may serve in the full comprehension of
the existing, relatedMX5-mediated processes, and itmay hopefully promote the development
of new MX5-mediated syntheses.

III. El mecanismo 1 tiene en cuenta la coordinación con una sola molecula de NbCl5 que se
daría con el Cl y la amina (no probable).

IV. El mecanismo 2 tiene en cuenta la coordinación con dos atomos de Nb. Similar a la
coordinación de NbCl5 con aminoácidos. (Fig.5 y Fig 6 del artículo 3. NbCl5-aminoacids).
La corroboración de las bandas en FTIR debería dar cuenta de esto. Duda hay liberación de
HCl lo que hace que los reusos sean tan bajos? No es catálisis heterogénea es homogénea?

V. yo he hecho unos cálculos teóricos pero no me da la capacidad de mi PC. Así que mejor
envío eso al brasilero. Hay mucho reporatdo con NbCl5 pero no explican cómo ocurren las
reacciones.
 CH3

HO
NH2

H3C
+ O
CH3 CH3
Cl

Cl Nb Cl
Cl

Cl

H2O

+
NH
HO
H3C O NH2
Cl
O
H3C Cl
Cl Nb Cl
Cl Nb Cl
Cl Cl
Cl
IV CH3 Cl

I CH3

H
H
O
N H C
O
H3C Cl
H
Cl Nb Cl O
Cl NH2
O
Cl H3C Cl

Cl Nb Cl
Cl

III Cl

II

Mecanismo I
Mecanismo II
 Remarks

Apparently, this reaction should proceed via nucleophilic substitution mechanism

on the carboxyl groups, right? However, the hydroxyl are not good leaving groups. In
addition, the direct reaction between amines and carboxyl acids should lead to the
equilibrium between their protonated and unprotonated forms, correct? In this sense, is
would be easy to react amines with carboxylic acids without extreme conditions, and just
by the interaction between the reactants and the catalyst? If the answer is no, we would like
to suggest it is possible that the catalyst should be a chlorine source for a first nucleophilic
substitution step on the carboxyl group (otherwise another source of chlorine like PCl5
would be needed – references 2 and 3), so then the RCOCl species would undergo a
necleophilic acyl substitution by amine (Mechanism III).

Mechanism III
I. See however that in this paper (reference n.1 in the e-mail) the Nb is bound to a carbon
atom and not to the nitrogen. But once you are sure that a lot of amines is necessary, the
excess of R’-NH2 reacting with carboxyl acids would lead to their protonated forms,
right? In this case, perhaps the ammonium should ease the chlorine release from the
catalyst (Mechanism IV), as the backwards reaction in the scheme 1 of the reference
number 5.

IV. As the papers you sent mentioned, the reaction between NbCl5 and amines would
release HCl. Also, in the mechanism IV would be possible to take into account the
interaction between the animes and Nb2Cl9+ as you pointed out, that could be neutralized
by RCOO- species, suppressing the catalyst recovering.

Mechanism IV
  Both mechanism III and IV suggests the existence of RCOCl species as
intermediates. Would them be possible to be detected?
 A way to distinguish the mechanism III and IV is by the formation of HCl.
The mechanism IV counts on a decreasing of pH in the initial steps. Could
this be confirmed?

II. I’m afraid that RCOO- are strong ligands to Nb, generating too stable species to proceed
with the reaction (paper number 2). Anyway, there is a chance for RCOCl species to not
be detected. Therefore, we would like to suggest the mechanism V, which is similar to
the DCC mechanism for amide synthesis from carboxylic acids and amines. It is also in
line with the excess of amine in order to generate the protonated forms. The mechanism
V should be an alternative in case you do not find any sign of RCOCl species.

Mechanism V