COORDINATION

COMPOUNDS
LEC-1
ADDITION COMPOUNDS

When two or more than two simple salts combine in a fixed proportion
by weight then the compound formed is known as molecular addition
compounds.
Addition compounds are two types
(i) Double salt.
(ii) Coordination Compound.
DOUBLE SALTS

Addition compounds which are formed by the combination of two or

more simple salts, and their aqueous solution shows the presence of all

its constituent ions are known as double salts .

K2SO4 + Al2 (SO4)3 + 24H2O → K2SO4. Al2(SO4)3. 24 H2O
K2SO4 + Al2 (SO4)3 + 24H2O → K2SO4. Al2(SO4)3. 24 H2O
• These are stable in solid state only but are broken down into
individual constituents when dissolved in water.
• Their solutions have the same properties as the mixture of individual
compounds .
• For example, when carnallite (KCl.MgCl2.6H2O) is dissolved in water it
exhibits the properties of KCl and MgCl2 .
COORDINATION COMPOUNDS

3KCN(aq) + Fe(CN)3(aq) → [Link](CN)3

Those addition compounds which retain their identity in solution are called
coordination compounds.
• The properties of their solutions are different than those of their
constituents.
• In such compounds there is complex ion which is a central metal ion
with Lewis bases attached to it through coordinate covalent bonds.
• In coordination compounds some of the constituent ions or molecules
lose their identity in compound formation and when dissolved in
water they do not break up completely into individual ions , rather
they furnish some new ions in the solution .
 Counter ions
C.M.I.
Ligands
K3 [Fe(CN)6] Coordination
Entity [Cu(NH3)4]SO4
No. of ligands
Coordination sphere
Coordination compounds

• Contains at least one central atom or ion.

• The central atom is surrounded by some electron pair donor groups called

as ligands.

• Central atom and the ligands have coordinate bond.

Central Atom
In a coordination entity–the atom/ion around which a fixed number of
ligands are bound in a definite geometrical arrangement, is called the
central atom or ion
LIGANDS
The neutral molecules, anions or cations which are directly linked with
central metal atom or ion in the coordination entity are called ligands.
The atom in ligand which donates electron pair is called as donor atom.

:
N O

H H
H H
H
DENTICITY
The number of sigma bonds formed by a ligand with a particular central
atom is called as denticity of the ligand.
On the basis of denticity ligands are classified into
(i) Monodentate
(ii) Bidentate
(iii) Tridentate
(iv) Tetradentate
(v) Pentadentate
(vi) Hexadentate
MONODENTATE
BIDENTATE

They can donate two electron pair to one central atom.

 AMBIDENTATE LIGANDS

They have two or more different donor atoms but during formation of
complexes one donor atom is attached to metal ion/atom are called
ambidentate ligands such as CN¯, CNS¯, NO2– , SCN– ions etc.

They cannot use all the donor sites simultaneously.

(i) CN¯ M ⎯ :CN: ¯

M ⎯ :NC: ¯
 COORDINATION NUMBER

Coordination number (CN) = No. of s-bonds formed by the central atom

C.N. = 6 , is most common , after that 4 then 2 .

Odd coordination number are shown in less number of complexes.

 OXIDATION NUMBER

It is the charge on the central atom or ion that will appear if all the ligands are

removed along with their donated electron pairs.

ILLUSTRATION Calculate oxidation state and coordination number.

(i) K4[Fe(CN)6]

(i) [Ni(CO)4]
(iii) [Co(en)3]3+

(iv) [Mg(EDTA)]2-
(v) [Co(en)2Cl2]+

(vi) [V(CO)6]-
(vii) [Co(CO)5]+

(viii) [Ag(NH3)2]+
 NAMING OF COORDINATION COMPOUNDS

In naming of complex following steps are followed.

(i) Like simple salts the cation is named first followed by anion.

(ii) In naming of complex part ligands are written first followed by the name

of central atom.

(iii)If more than one ligands are present then the ligands are written in

alphabetical order before the name of central atom.

(iv) Prefixes mono , di , tri etc are used to indicate the number of one kind of

ligands in complex.

When the name of ligand itself has numerical prefix or use of numerical

prefix can create confusion then second set of prefixes are used.

No. Prefix Second set of prefix

2 di bis

3 tri tris

4 tetra tetrakis
(v) Oxidation number of central atom is indicated in Roman numerals in the

parenthesis after the name of metal.

(vi) If any water of crystallization then it is written in the name of complex.

 IUPAC Naming of ligands
Based on the charge of
ligand

Positively charged Negatively charged Neutral

ligands ligands Ligands
Negatively charged ligands

_____ ide → _____ ido

_____ ite → _____ito

_____ ate → _____ ato

Cl-

SO3-2

C2O4-2

SO4-2
Common Name IUPAC Name Formula
methyl isocyanide Methylisocyanide CH3NC
triphenyl phosphine triphenyl phosphine PPh3
Pyridine pyridine C5H5N (py)
Ammonia ammine NH3
methyl amine methylamine MeNH2
Water aqua or aquo H2O
Carbonyl carbonyl CO
Thiocarbonyl thiocarbonyl CS
Nitrosyl nitrosyl NO
Fluoride fluorido F–
Chloride chlorido Cl–
Bromide bromido Br–
 Nitrate Nitrato NO3–
Amide amido NH2–
Imido imido NH2–
Nitride nitrido N3–
Azide azido N 3–
Hydride hydrido H–
Oxide oxido O2–
Peroxide peroxido O22–
Superoxide superoxido O2 –
Acetate acetato CH3COO–
Iodide iodido I–
Neutral ligands Names of neutral ligands is unchanged except

H2O : aqua

NH3 : ammine

NO : nitrosyl

CO : carbonyl

CS : thiocarbonyl

P4 : tetraphosphorous

O2 : dioxygen.
Positively charged ligands

Names of positively ligands are prefixed “ium”

NO+ : nitrosylium

NO2+ : nitronium

NH2NH3+ : hydrazinium
For naming ambidentate ligands , write name of donor atom after the name

of ligand.
 Naming of Central Atom

Based on the charge on

coordination sphere

Positively Negatively
Neutral
charged charged
If central atom is in cationic or neutral coordination sphere then normal

name is of central atom is used in naming.

If central atom is in anionic coordination sphere then its name is

modified and suffixed “ate”.

Metal Name in Neutral or Name in anionic sphere
cationic sphere
Zn
Al
Co
Ni
Pt
Ag
Hg
W
Metal Name in Neutral or Name in anionic sphere
cationic sphere
Fe
Au
Cu
Cr
Co
Illustrations Write the name of the following complexes.

(i) K4[Fe(CN)6]

(ii) [Ni(CO)4]
(iii) [Ag(NH3)2]+

(iv) [Ni(CN)4]2-
(v) [RhCl(PPh3)3]

(vi) K2[HgI4]
 III
(vii) [Cr(CN)6][Co(CN)6]

(viii) [Pt(NH3)2Cl2]
 III
(ix) Fe4[Fe(CN)6]3

(x) Fe[Fe(CN)6]
EFFECTIVE ATOMIC NUMBER (EAN)
Effective atomic number is the effective number of electrons around
the nucleus of central atom.
Effective Atomic Number (EAN) = No. of electron present on the
metal atom /ion + No. of electrons donated by ligands to it.
Effective Atomic Number (EAN)
= Atomic no. of central metal – Oxidation state of central metal + No.
of electrons donated by ligands.
(EAN) = Z - (O.S.) + 2(C.N.)
ILLUSTRATION Calculate EAN.

(i) K4[Fe(CN)6]

(ii) [Ni(CO)4]
(iii) [Co(en)3]3+

(iv) [Fe(CO)5]
(v) [Co(CO)4]-

(vi) [V(CO)6]-
(vii) [Co(CO)5]+

(viii) [Ag(NH3)2]+

(ix) [Pt(NH3)2Cl2]
 Sidwick’s EAN rule
Electron pair are added around the central atom till its EAN becomes equal
to atomic number of the noble gas in the period of the central atom.
3d – series : 36Kr

4d – series : 54Kr

5d – series : 86Rn
Metal carbonyls and nitrosyls generally follow EAN rule.
ILLUSTRATION Calculate x.

(i) [Ni(CO)x]

(ii) H[Co(CO)x]
VBT for complexes
(i) The central metal atom or ion in the complex makes available an
adequate number of empty orbitals ,equal to the coordination number
of the central ion, for the formation of coordinate bonds.
(ii) The appropriate atomic orbitals (s, p and d) of the metal hybridize to
give an equal number of new orbitals of equivalent energy, called hybrid
orbitals.
(iii) The hybrid orbitals are directed towards the ligand positions
according to the geometry of the complex.
(v) The d orbitals involved in the hybridisation may be inner, viz.,
(n–1)d orbitals or the outer, viz., nd orbitals.
(vi) The empty hybrid orbitals of metal atom or ion overlap with the fully
filled orbitals of the ligand, forming the ligand-metal coordinate bond.
C.N. Hybridisation Orbitals used in hybridisation

6
Donor ability of ligand:
ILLUSTRATION Determine the hybridization

(i) K4[Fe(CN)6]
(ii) [Ni(CO)4]
(iii) [Co(en)3]3+
(iv)[Ag(NH3)2]+
(iv) [Fe(NH3)6]+2 ms = 4.9 BM
(v) [Ni(Cl)4]2-
(vi) [FeF6]3-
(v) [Pt(Cl)2(NH3)2] spin only magnetic moment = 0
 Failures of Valence Bond Theory
➢ Not able to explain colour of complexes.
➢ No differentiation between SFL & WFL.
➢ Does not explain stability completely.
➢
 Crystal Field Theory
➢ The interaction between the ligand and central atom is purely electrostatic in
nature.
➢ There is no overlap between the orbitals of central atom and ligands.
➢ Ligands are considered –ve point charges , in case of neutral ligand the –ve
end of dipole is considered
In an isolated atom all the d-orbitals are degenerate (i.e of equal energy)
➢ In complexes, due to unsymmetric field, degeneracy is lost and d-
orbitals are split into different energy orbitals.
➢ In spherically symmetrical field energy of all the d- orbitals is changed
equally.
 CRYSTAL FIELD THEORY for OCTAHEDRAL COMPLEXES
• Ligands are assumed to be approaching along coordinate axis.
Do = Crystal field splitting energy in octahedral complexes.

P = Pairing energy.

Ligands for which Do > P are called as strong field ligands (SFL)

Ligands for which Do < P are called as weak ligands (SFL)

SPECTROCHEMICAL SERIES
Series in which ligands are arranged in increasing order of magnitude of Do

I- < Br- < SCN- < Cl- < S-2 < F- < OH- < C2O4-2 < H2O

< NCS- < EDTA-4 < NH3 < en < bipy < NO2- < PPh3 < CN- < CO
General order of strength.

X < O < N < C

 Crystal field Stabilisation energy (CFSE)
It is measure of decrease in energy due to crystal field splitting
Measured wrt to Bari Center
Bari Centre : It is the mean energy level.
 CRYSTAL FIELD THEORY for TETRAHEDRAL COMPLEXES
• Central atom is assumed to be present at the center & ligands are assumed to be
approaching along the alternate corners of the cube.
• In tetrahedral field non-axial orbitals are repelled more than axial

orbitals, because they are more closer to the ligands.

• For same central atom and ligands

Dt = 4 Do
9
• Only four ligands are present so field is decreased by a factor of 2/3.
• No orbital is experiencing head on repulsion from ligands , thus repulsion
from ligands is decreased by a factor of 2/3.
• Due to small magnitude of Dt , tetrahedral complexes are high spin and
less stable.
 CRYSTAL FIELD THEORY for Sq. Planar COMPLEXES
A square planar complex can be considered in same way as an octahedral
complex.
Let us consider Ni2+ (3d8) & 6 CN- are approaching along coordinate axes.
Due to more repulsion experienced by the dx2-y2 further splitting takes
place.
Due to this dz2 gets completely filled and ligands along z-axis are
repelled away and cannot contribute to complex formation.
SQUARE PLANAR COMPLEXES ARE FORMED BY

• Strong field ligands with central atom in3d8configuration.

• By all the ligands with central atom in 4d8 & 5d8 configuration.

All complexes of following ions are always square planar.

Rh+ Pd+2 Ag+3

Ir+ Pt+2 Au+3

 FACTORS AFFECTING D
(i) Nature of ligands : A SFL causes more splitting than a WFL for same
ion/atom.
(ii) Oxidation state of central atom : As oxidation state of central atom
increases D increase.
(iii) Period of central atom: On moving down the group D increases.
D
[Co(NH3)6]3+ 300 KJ/mole
[Rh(NH3)6]3+ 400 KJ/mole
[Ir(NH3)6]3+ 500 KJ/mole
For 4d & 5d Series Metals All The Ligands Are Strong field ligands
For Co3+ H2O & C2O42- are strong field ligands (SFL)
ILLUSTRATION Determine the geometry hybridization

(i) [Rh(PPh3)3Cl]
(ii) [AuCl4]-
(iii) [Cu(CN)4]3-
(iv) [Pt(NH3)2Cl2]
(v) [Ni(CN)4]2-
(vi) [Ni(CO)4]
(vii) [NiCl4]2-
(viii) [Ni(dmg)2]
(iv) [Co(H2O)2((C2O4)2]-
(v) [Co(H2O)6]2+
(v) [Ni(NH3)6]2+
For compounds containing SFL as well as WFL
(i) If more than 50% of C.N. is satisfied by SFL then consider the
case of SFL.
(ii) If more than 50% of C.N. is satisfied by WFL then consider the
case of WFL.
(viii) Na2[Fe(CN)5(NO)]2-
(ix) [Fe(H2O)5(NO)]2+
 COLOUR

Colour of a substance is due to the absorption of light in the visible

part of the electromagnetic spectrum (400 to 800 nm) and transmission
or reflection of the rest of the light.

e-
The colour observed is complimentary to colour absorbed.

V/ I
B

R G

O Y
 COLOUR OF COMPLEX

According to CFT colour of a complex is due to d-d transition.

e-
ILLUSTRATION A complex [M(H2O)6]2+ absorbs a wavelength of 5000 Ao .

Then determine Do
(ii) Name three ligands whose complex absorbs a wavelength less than
5000 Ao .
(iii) Name three ligands whose complex absorbs a wavelength more than 5000 Ao .
CHARGE TRANSFER

Some complexes are not coloured due to d-d transition, but they are

coloured due to charge transfer.

Colour due to charge transfer is more intense than d-d transition.

Eg. KMnO4 violet colour due to charge transfer.

 STABILITY OF COMPLEXES

The stability of a coordination compound [MLn] is measured in terms of the

stability constant (equilibrium constant).

M(H2O)n + nL MLn + nH2O

Some important generalisation regarding stability constants :

(i) Greater the charge density on the metal greater is the stability of

the complex.

For the divalent ions of the first row transition elements,

irrespective of the ligand involved, the stabilities vary in the Irving-

Williams order

MnII < FeII < CoII < NiII < CuII > ZnII
(ii) A stronger field ligand forms more stable comlex than a
weaker field ligand.

(iii) The stability also depends on the formation of chelate rings.

ILLUSTRATION Compare stability

(i) [FeF6]4- [Fe(H2O)6]2+ [Fe(NH3)6]2+ [Fe(CN)6]4-

(ii) [Cr(NH3)6]3+ [Cr(NH3)4(en)]3+ [Cr(NH3)2(en)2]3+ [Cr((en)3]3+
(iii) [Co(NH3)6]3+ [Rh(NH3)6]3+ [Ir(NH3)6]3+
(iv) [Cr(NH3)6]3+ [Cr(H2O)6]3+ [Cr((en)3]3+ [Cr(CN)6]3-
 Werner’s theory :

For every central atom there exists two types of valences

(i) Primary valency

(ii) Secondary valency

Every central atom has fixed number of primary and secondary valencies.

Every central atom has a tendency to satisfy both types of valencies for that

sometime a negatively charged species may play a dual role.

Primary valency :

It is equal to oxidation number of central atom.

✓ Satisfied by simple anions .

✓ Ions satisfying only primary valency are are ionisable and written

outside the coordination sphere.

✓ They are non-directional

✓ represented by ‘…………’
 Secondary Valency : -
It is equal to coordination number of central atom.
✓ Can be satisfied by ions or central molecules .
✓ Species satisfying secondary valency are always written inside the
coordination sphere.
✓ It is non-ionisable
✓ It is directional in nature hence there exists a definite shape and
geometry about central atom.
✓ Represented by ‘___________’
Eg : [Cr(H2O)5Cl]Cl2
1o valencies are satisfied by
2o Valencies are satisfied by
For formula CrCl3.6H2O , possible complexes

A:

B:

C:

D:
Now we differentiate b/w A, B, C, & D, by
(i) Precipitation reactions
𝐀𝐠𝐍𝐎𝟑
Complex(aq) → 𝐀𝐠𝐂𝐥 ↓
𝐞𝐱𝐜𝐞𝐬𝐬

A:
B:
C:
D:
(ii) Conductivity Measurement
under identical Condition
Conductivity  No. of ion
 charge on the ions.
Conductivity order :
(iii) Measurement of colligative prop.
p (osmotic Pressure)  No. of particles.
p:
 𝑯𝑨
(iv) Ion exchange method complex ppt (s) + HCl
Ions outside coordination sphere are exchanged where as ions
inside the coordination sphere are not exchanged.
 Types Of Ligands

Non-classical ligands or
Classical Ligands
π-acid acceptor ligands
Ligands which only can donate When ligands can donate e--pair to
e--pair to central atom but can’t central atom and simultaneously
back accept electron pair from accept electron pair from central
central atom. atom.
They have no vacant orbital. They have vacant orbital.
Eg. OH- , Cl- ,dmg- , F- etc . Eg. CO ,PPh3 ,CN- etc .
 Organometallic Compound
A compound which has bond between carbon and metal are termed as
organometaalic compound.
Eg- Grignard’s reagent (RMgX)
s–bonded complex

s bond between metal and carbon atom.

Eg. R–Li
Pb(C2H5)4
p–bonded complex
Metal is bonded with p– electron donor ligands like benzene..

Eg. [Cr(η6 –C6H6)2]

Eg. Ferrocene [Fe(η5–C5H5)2]

Fe2+
Eg. Zeise’s salt K[Pt(η2–C2H4)Cl3]

M
 Metal carbonyls

In metal carbonyls CO donates an electron pair into orbitals of metal

M :CO

The metal can back -donate from its filled orbitals into the vacant orbital of CO

M :CO
In metal carbonyls metal has s as well as p bond with the metal.

CO has 14 electron thus it is an isostere of N2 .

For simplicity we can consider its MO similar to N2

s1s < s* 1s < s2s < s*2s < (p2px = p2py) < s2pz < (p*2px = p*2py) < s*2pz
Synergic Bonding

As the formation of pie-bond increases, the tendancy for formation of

sigma-bond increases by creating –ve charge at the ligand and +ve at the

central atom, therefore strength of both the bonds increases. This type of

bond is called as synergic bond.

Extent of backbond α (charge on the central atom)

As the extent of backdonation increases

No. of e- in ABMO of CO increases.

Thus Bond order of C – O bond decreases.

Thus Bond length of C – O bond increases.

Thus Bond order of M – O bond increases.

Thus Bond length of M– O bond decreases.

ILLUSTRATION

Compare extent of back bond, M-C and C-O bond orders and lengths in

(A) [Ni(CO)4] [Co(CO)4]- [Fe(CO)4]2-

(B) [Cr(CO)6] [V(CO)6]- [Mn(CO)6]+
Structure of metal carbonyls

[Ni(CO)4]
[Cr(CO)6]
[Fe(CO)5]
Metal carbonyls obey EAN rule.

If in a carbonyl EAN rule is not followed then the carbonyl achieves desired

EAN by reaction

(i) If in a carbonyl EAN > (EAN)noble gas

Then it loses e- to get desired EAN .

Eg. Co(CO)5 → [Co(CO)5]- + e-

(ii) If in a carbonyl EAN < (EAN)noble gas

Then it either gains an e- or dimerise to get desired EAN .

Eg. Co(CO)4 + e- → [Co(CO)4]+

2Co(CO)4 → Co2(CO)8
Co2(CO)8
Mn2(CO)10
ISOMERS
Compounds with same molecular formula but different properties are
isomers.
Isomers

Structural Isomers Stereoisomers

STRUCTURAL ISOMERS
They have same molecular formula but different structural formula.
Coordination compounds exhibit five types of structural isomerism
1. Ionisation isomerism
2. Solvate / hydrate isomerism
3. Linkage isomerism
4. Coordination isomerism
5. ligand isomerism
 STEREOISOMERS ISOMERS

Isomers that have same molecular and structural formula but have
different orientation of the atoms/groups in space .

Stereoisomers have same connectivity of atoms and groups.

Stereoisomers have remarkably different physical, chemical and biological

properties.
 Structural Isomers

Ionisation isomerism

Two or more than two compounds with same molecular formula but produces
different simple ions upon ionisation.

Ex. CoClBr.5NH3
 Structural Isomers

Solvate/ hydrate isomerism

Two or more than two compounds with same molecular formula but different
number of H2O molecules as ligand.

Ex. CoCl3.6H2O
Structural Isomers
Linkage isomerism

Isomerism which arises due to different donor atoms of an ambidentate

ligand.

Ex. Na3[Co(SCN)Cl5]
Structural Isomers

Coordination isomerism

Possible when both cationic and anionic parts are complex in nature.
It is due to exchange of ligands between cationic and anionic complex
parts.
Ex. CrCo(CN)6(NH3)

[Cr ( ) ( ) ] [Co ( ) ( ) ]
Structural Isomers

Ligand isomerism

Arises due to isomerism about the ligands.

NH2
NH2 NH2 NH2
Structural Isomers

Ligand isomerism

Arises due to isomerism about the ligands.

NH2
NH2 NH2 NH2
 Stereoisomers Isomers

Geometrical Isomers Optical isomers

 
GEOMETRICAL ISOMERS

This type of isomerism arises in heteroleptic complexes due to different

possible geometric arrangements of the ligands.

Conditions for exhibiting geometrical isomerism

1. Restricted Rotation
2. Different groups at the ends of the restricted rotation.
3. Distance between the groups must be different in isomers.
 Optical Isomers A coordination compound which can rotate the plane
of polarized light is said to be optically active.

When the coordination compounds have same formula but differ in their
ability to rotate directions of the plane of polarised light are said to exhibit
optical isomerism and the molecules are optical isomers
Condition for a compound to be optically active
1. No plane of symmetry (POS)
2. No center of symmetry (COS)
Representations used

Monodentate ligands : a , b , c , d , etc.

Bidentate ligands :
Symmetrical ligands : (AA) , (BB) , (CC) , etc.

Unsymmetrical ligands : (AB) , (BC) , (CD) , etc.

Examples :
O O O– H3C N
C O
C—C NH2
O O O C OH
H3C N
SQUARE PLANAR COMPLEXES

Groups/atoms at an angle of 180° are called as trans pairs.

Square planar complexes will have plane of symmetry, thus they
cannot exhibit optical activity.

Square planar complexes may exhibit geometrical isomerism.

Ma4 type complexes

Geometrical Isomerism :
Ma2b2 type complexes

No. of Geometrical Isomers :

M(AA)b2 type complexes

Geometrical Isomerism :
Mabcd type complexes

No. of Geometrical Isomers :

M(AA)(BB) type complexes

No. of Geometrical Isomers :

M(AB)(CD) type complexes

No. of Geometrical Isomers:

Question:

[Pt(NH3)2Cl2] is called platin. The number of isomers of platin are

Question:

The number of isomers of K2[PtFBrICl] are

Octahedral Complexes
Ma6 type of Complexes

Geometrical Isomerism:

Optical Isomerism:
Ma4b2 type of Complexes

POS : POS :

No. Of Geometrical isomers :

Ma3b3 type of Complexes

POS : POS :

No. Of Geometrical isomers :

M(AA)b4 type of Complexes

POS :

No. Of Geometrical isomers :

M(AA)2b2 type of Complexes

POS :
No. Of Geometrical isomers :
No. of Optically active isomers :
Total No. of stereoisomers :
M(AA)3 type of Complexes

POS :
Geometrical isomers :
No. of Optically active isomers :
Total No. of stereoisomers :
M(AB)3 type of Complexes

POS :
POS :
Geometrical isomers :
No. of Optically active isomers :
Total No. of isomers :
 Tetrahedral complexes

No Geometrical isomers as distance between the groups is always same

May exhibit optical activity if POS & COS is absent

Ma4 type complex

POS :
Ma3b type complex

POS :
Ma2b2 type complex

POS :
Mabcd type complex

POS :
M(AA)b2 type complex

POS :
M(AA)2 type complex

POS :
M(AB)2 type complex

POS :
Question:
The number of isomers for

1. [Co(en)2Cl2]
2. Na2[Pt(SCN)2Cl2]
3. [Co(NH3)3Cl3]
4. [Co(en)3]3+