Magadh University, Bodh-Gaya

Dr. Partha Pratim Das

Assistant Professor
P.G. Department of Chemistry
Magadh University, Bodh-Gaya

E-Content Title: Metal Nitrosyls, Metal-Dinitrogen and Metal-

Dioxygen Complexes

Stream: M. Sc. (2nd Semester)

Email id: mail.to.parthapratimdas@gmail.com

 Metal- π Complexes
Metal Nitrosyls: Metal nitrosyls are the complexes that contain nitric oxide (NO) bonded to a
metal center, usually transition metals. Metal complexes having nitrosyl ligands only are labeled
as isoleptic nitrosyls. They are very rare, perhaps represented by [Cr(NO)4] alone. There are
various kinds of nitrosyl complexes known so far, which vary in respect of co-ligand, structure
and nature of bonding. Linear, bent, doubly, triply and even quadruply bridged modes of
coordination are known.
Preparation: Unlike the carbonyls, nitric oxide complexes cannot be prepared directly
using excess NO at high temperature and pressure. Several methods of preparation of nitric oxide
complexes are available;
1. Addition of NO or substitution by NO: Metal nitrosyl complexes can be prepared via
many routes, but direct formation from nitric oxide gas is much more common. For example:
[Co2(CO)8] + 2NO → 2[Co(CO)3NO] + 2CO
[Ni(Ph3P)2(CO)2] + 2NO → [Ni(Ph3P)2(NO)2] + 2CO
[Cr(CO)6] + 4NO → [Cr(NO)4] + 6CO
[(η5‐C5H5)Fe(CO)2]2 + 2NO → [(η5‐ C5H5)Fe(CO)(NO)]2 + 2CO
[Co(OPPh3)2X2] + 2NO → [Co(NO)2(OPPh3)2X2]
[Mn(CO)5I] + 3NO → [Mn(CO)(NO)3] + 4CO + I
[Fe(CO)5] + 2NO → [Fe(CO)2(NO)2] + 3CO
In substitution reaction three CO ligands are replaced by two NO ligands or one NO can
replace one CO plus one halogen atom.

2. Methods involving nitrosonium salts (NO+): NOBF4, NOPF6 or NO[HSO4] can be

used to add or to substitute in other complexes
[Ir(CO)(PPh3)2Cl] + (NO)BF4 → [Ir(CO)(NO)(PPh3)2Cl]BF4
[RhCl(CO)(PPr3)2] + NO+ → [RhCl(NO)(CO)(PPr3)2]+
[Rh(CNR)4]+ +NO+ → [Rh(CNR)4(NO)]2+

3. From nitrosyl halides:

Et4N[HB(3,5‐Me2‐pz)3Mo(CO)3] + ClNO → [HB(3,5‐Me2‐ pz)3Mo(CO)2(NO)] + CO +
[Et4N]Cl

4. From N-nitrosamides:
[HMn(CO)5] + p‐ tolyl-SO2N(Me)(NO) → [Mn(CO)4(NO)] + CO + p‐ tolyl-SO2NHMe

5. From nitrite salts:

Na[Co(CO)4] + Na(NO2) + 2HOAc → [Co(CO)3(NO)] + CO + 2NaOAc + H2O

6. From nitronium (NO2+) salts:

[(η5‐C5H5)Re(CO)3] + [NO2]PF6 → [(η5‐ C5H5)Re(CO)2(NO)]PF6 + CO2
 Bonding and Structure: Nitric oxide (NO) has total 15 electrons and 11 electrons in
valence shell. Most of the metal nitrosyl complexes can be viewed as derivatives of the nitrosyl
cation (NO+) or anion (NO−). The nitrosyl cation (with a bond order of 3) is isoelectronic with
carbon monoxide, thus the bonding between a nitrosyl ligand and a metal follows the same
principles as the bonding in carbonyl complexes. In order to rationalize the nature of the bonding
between metal center and the nitrosyl ligand, we must understand molecular orbital diagram for
the nitrosyl ligand first. The bond order of neutral nitrosyl and anion are 2.5 and 2, respectively.

Molecular orbital diagram of nitric oxide (NO)

After looking at the molecular orbital diagram for NO, one can immediately recognize the
difference from the carbonyl ligand that there is one extra electron in the π*-orbital. This
suggests that NO ligand can be one, two or three electron donors, depending upon the type of
orbital used in bonding.

Nature of σ and π overlap in metal nitrosyl complexes

If the electron present in π*-orbital resides on NO, i.e., not transferred to the metal center,
nitrosyl ligand would behave as a two-electron donor, and the nature of metal complex should be
paramagnetic. There are some nitrosyl complexes of iron and cobalt such as [Fe(NO)2(CO)2] and
[Co(NO)(CO)3], which were thought to be derived from neutral NO ligand but these compounds
are diamagnetic in nature; and therefore do not contain unpaired electrons. This suggests that the
nitrosyl ligand is not neutral in these complexes.
Moreover, there are also many complexes like [Cr(NO)(CN)5]3− and [Mn(NO)(CN)5]2−, which
are actually paramagnetic and were also thought to be having neutral nitrosyl ligand. However,
in the later years, it was found that the unpaired electron of the nitrosyl group is actually
transferred to the metal center making NO as NO+ ligand. Thus, we can say that the coordination
of neutral nitrosyl is highly unlikely.

 Complexes containing NO+: Nitric oxide molecule can easily release the odd electron
from its anti-bonding molecular orbital to form a stable nitrosonium ion (NO+). It is clear from
the comparison of the IR absorption spectra of free NO (vNO 1880 cm-1) with those of salts
containing NO+ ion (vNO+ = 2200-2300 cm-1). This can be explained in terms of increased bond
order from 2.5 to 3, and consequently the force constant value. Most of the metal nitrosyls exist
with nitrosyl ligand as three electron donor.
Most of such complexes obey EAN rule, if we assume that NO ligand is a 3-electron donor. For
example, the effective atomic number (EAN) of Fe in [Fe(NO)2(CO)2] is 26 + 2X3 + 2X2 = 36,
which is the atomic number of the next inert gas. Similarly, for Mn in [Mn(CO)(NO)3] is 25 +
lX2 + 3X3 = 36.
The ligation of NO to the metal in these complexes follows the following steps:
1. Initial complexation with the metal; NO loses one electron which reduces the metal by
one unit and gets converted to NO+.
2. In the second step NO+ donates a pair of electrons to the metal to get coordinated to the
metal like CO. In this way, NO in its nitrosonium complexes act as 3-electron donor. Back-
bonding occurs between metal and ligand. Back donation of electron from filled d-orbital of
metal to π*-orbital of NO would result in a considerable decrease in the nitrogen-oxygen bond
order.
 IR absorption frequency of NO+ in nitrosonium complexes (in which NO+ is present as a
coordinated cation) falls between 1600-1900 cm-1 which is much lower than the absorption
frequency of NO+ in its ionic salts (containing NO+ as a free cation) which falls between 2200-
2300 cm-1. Extent of lowering of absorption frequency of NO+ is much greater compared to
similar lowering of vCO in case of metal carbonyls, establishing that π back-bonding in
nitrosonium complexes is much greater than in metals carbonyl, which is further increased by an
accumulation of negative charge on nitrosonium complexes.

 Complexes containing NO−: Nitric oxide molecule can also accept an electron from the
metal center to its anti-bonding molecular orbital forming a NO− ion. The metal center in this
process would get oxidized from Mn+ to M(n+1)+ ion. The NO− then donates two electrons through
N atom to the resulting M(n+1)+ to form a σ-coordinate bond. Total number of electrons donated
by NO, in this case, would be effectively one. Infrared absorption wave numbers of NO− in metal
nitrosyl complexes are found in much lower range than NO, which can be explained in terms of
complete transfer of one electron from dπ orbital of metal center to anti-bonding molecular
orbital on nitrosyl ligand.
During the formation of [Co(CN)5(NO)]3− and [Co(NH3)5(NO)]2+ complexes (passing
NO through amine and cyanide salts of Co2+), the CoII gets converted into low spin CoIII with t2g6
configuration. Both of these complexes, in respect of charge and magnetic moment, resemble
[Co(CN)5Br]3− and [Co(NH3)5Cl]2+, respectively.

Bonding Modes: Three principle modes of bonding by NO are commonly found:

(i) Terminal, Linear M-N-O group: Here NO may be regarded formally as a three electron
donor as NO+, However the M-N-O angle in such complexes have been found to vary from 165-
180o. The vNO in these cases usually fall in the range 1650-1900 cm-1.
(ii) Bent M-N-O group: Here the angles vary between 120-140o. Here the NO molecule may
be considered as 1 electron donor NO−. vNO in these cases usually fall in the range 1525-1690
cm-1.
(iii)Bridging NO groups: Doubly, triply and even quadruply bridged nitric oxide complexes
are known. vNO in bridging complexes occur in the range 1480-1510 cm-1 for µ2 bridge and ~
1320 cm-1 for µ3 bridge. Both symmetric and asymmetric bridges are known.
Structure: The structure of metal nitrosyls can mainly be classified into three categories; first as
the metal-complex systems that contain NO as a terminal ligand only, the second one as having
only bridging nitrosyl group, and the third one with nitrosyl groups with the terminal as well as
bridging profile.
(i) Metal complexes with terminal nitrosyl: The NO group as a monodentate ligand in
metal complexes acts either as a 12-electron unit (when NO− forms a single bond with the metal
center and M−N−O unit is bent), or as a 10-electron unit (when NO+ forms a multiple bonds with
the metal center and M−N−O unit is linear). Example;

(ii) Metal complexes with bridging nitrosyl: In some of the metal nitrosyl complexes, all
NO groups are present in bridging mode. For example;

(iii) Metal complexes with the terminal as well as bridging nitrosyl: In some of the metal
nitrosyl complexes, NO groups are present in the terminal as well as in bridging mode. Some of
the common examples are:

Reactions of metal nitrosyl complexes:

(1) Reduction of metal nitrosyls:

 (2) Formation of carbon-nitrogen bonds:

(3) Reactions of nitrosyls with electrophiles:

(4) Nucleophilic attack:

Metal Dinitrogen Complexes: Metal dinitrogen complexes are the coordination compounds that
contain the dinitrogen ligand (N2) attached to a metal center. The first complex known of
dinitrogen was [Ru(NH3)5(N2)]2+.

Bonding: Molecular orbital diagram for N2 is given below;

N2 molecule is isoelectronic with CO and NO+, but it doesn’t form large number of metal
complexes like them as it is a poor ligand and due to the lack of polarity cannot act as a strong π-
acceptor. N2 ligand is neither a good σ-donor nor good π-acceptor.

Different bridging modes of N2 ligand are the following;

Most common binding mode of dinitrogen ligand with transition metal center is end-on i.e. like
CN-, CO and NO etc. End-on bonding involves the donation of the lone pair of N2 to the empty
metal orbital and back-donation from filled metal d-orbital to the empty π* orbitals. In side-on
bonding, electron donation occurs from π and σ bonding molecular orbitals of N2 to the empty
orbitals of the metal and back-donation of electron density from filled orbitals of the metal to the
π* molecular orbital of the N2 ligand. Though side-on bonding mode is quite common in metal-
acetylenes and metal-olefins, there are very few reports of side-on bonded dinitrogen complexes.
In [Ru(NH3)5(N2)]2+, Ru−N bond length in Ru−N−N unit is shorter than Ru−N bond length in
Ru−NH3 unit implying that there is some extent of back-bonding from filled d-orbital the metal
center to the empty π* molecular orbital of N2. This is also obvious from the vibrational Raman
stretching frequency of free N2 (2331 cm−1) and infrared active stretching frequency of metal
coordinated N2 (2105 cm−1) in [Ru(NH3)5(N2)]Cl2 complex.

Structure: Structures of metal-dinitrogen complexes can mainly be classified into two

categories;
(i) Metal complexes with end-on dinitrogen: N2 usually binds to metals as an end-on
ligand. Such complexes are usually analogous to related CO derivatives.
 (ii) Metal complexes with side-on dinitrogen: In some of the metal-dinitrogen complexes,
N−N vector is perpendicular to the M−M vector.

Preparation:
i) Direct formation of Metal-dinitrogen complexes from N2 is very common:

ii) From compounds containing chains of nitrogen atoms:

iii) Preparations where two nitrogen atoms are combined to give a dinitrogen group:

Reactions:

(i) Displacement of dinitrogen ligand by some other groups:

(ii) Reactions of bonded N2 with Lewis Acids:

 (iii) Formation of metal-hydrazido complxes from ligating N2:

(iv) Formation of carbon-nitrogen bonds:

Metal Dioxygen Complexes: Metal dioxygen complexes are the coordination compounds which
contain O2 ligand attached to a metal center. Most of the metal-dioxygen complexes are
synthesized by the reaction of gaseous molecular oxygen with complexes (having d7, d8, or dl0
electronic configuration) in solution. Primary reason for analyzing these types of compounds is
presence of oxygen-carrying proteins e.g. myoglobin, hemoglobin, hemocyanin, and hemerythrin
etc. Many transition metals form complexes with O2 reversibly. Binding of O2 is the first step in
many important phenomena, such as cellular corrosion, respiration and in industrial chemistry.

Bonding: Molecular orbital diagram for O2 is given below;

Experimental results show that bent structure of the dioxygen unit in oxyhemoglobin is actually
diamagnetic in nature; which suggests that π*2px and π*2py orbitals are not completely degenerate
in the complex as they are in free O2. Linear M−O−O structure would result in a degenerate set
of π*2px and π*2py orbitals with a triplet state. Different bridging modes of O2 ligand are given
below.

O2 ligand binds to a single metal center either end-on (η1) or in a side-on (η2) manner. Dioxygen
adducts derived from Co2+ and Fe2+ complexes of porphyrin exhibit these bonding mode.
Hemoglobin and myoglobin are two famous examples and many other synthetic analogs have
been reported which behave in a similar manner.
Binding of O2 is usually described as an electron transfer from the metal (II) center to give
superoxide (O2−) complexes of metal (III) centers for mononuclear complexes. The η2-bonding is
the most common mode seen in the coordination chemistry of dioxygen. Complexes containing
η2-O2 ligands are common, but most of them are generated using hydrogen peroxide, not O2.

Vaska's complex reversibly binds O2 as the following;

[IrCl(CO)(PPh3)2] + O2 ⇌ [IrCl(CO)(PPh3)2O2]

The conversion is described as a 2 electron redox process: Ir (I) converts to Ir (III) as dioxygen
converts to peroxide. Since O2 has a triplet ground state and Vaska's complex is a singlet, the
reaction is slower than when singlet oxygen is used.

However, O2 can bind to one metal of a bimetallic unit via the same modes discussed above for
mononuclear complexes. Well-known example in nature is hemerythrin, which features a di-iron
carboxylate that binds O2 at one Fe center. In nature, dinuclear dioxygen complexes with various
possible binding modes, depending on the degree of electron-transfer from the dimetallic unit,
are often found in copper complexes.

Structure: Structures of metal-dioxygen complexes can mainly be classified into two categories;

(i) Mononuclear metal-dioxygen complexes: As a ligand, O2 can bind to a single metal-

center either as an end-on ligand or as a side-on ligand. For example;
 (ii) Binuclear metal-dioxygen complexes: In binuclear metal-dioxygen complexes, the O2
molecule can bind either to one or both metals center as an end-on/end-on, end-on/side-on and
side-on/side-on ligand. For example;

Preparation:
(i) Formation of mononuclear dioxygen adduct with/without displacement of ligands:

(ii) Formation of dimer or binuclear dioxygen adduct:

(iii) Displacement of free oxidized ligand:

Reactions:
(i) Displacement of molecular oxygen by some other ligand:

(ii) Formation of complexes of oxidized substrates: