Isom

eris

m –

Ster

eois

omer

s:

Com

bina

tion

of C

hela

teR

ings

(∧, ∆

)C

oED

TA-

Not

cop

lana

r, no

t con

nect

ed a

t the

sam

e at

om

R1:

R2,

R3,

R4,

R5

XR

2: R

1, R

3, R

4, R

5

XX

XX

∆∧

∧

∧∆∧

, ∧

∧∆

, or ∆

∧∧

∆∧

6 C

N ;

Oct

ahed

ron,

Trie

thyl

ente

traa

min

e

H2N

H NN H

NH

2

Isom

eris

m –

Ster

eois

omer

s: L

igna

dR

ing

Con

form

atio

n

S S

∆ R R

∧

S S

∧ R R

∆

Isom

eris

m –

Ster

eois

omer

s: L

igna

dR

ing

Con

form

atio

n

Che

late

Rin

g C

onfo

rmat

ion

(λ, δ

)

6 C

N ;

Oct

ahed

ron,

Trie

thyl

ente

traa

min

e

Isom

eris

m –

Ster

eois

omer

s: L

igna

dR

ing

Con

form

atio

n

Che

late

Rin

g C

onfo

rmat

ion

(λ, δ

)

Isom

eris

m –

Con

stitu

tiona

l Iso

mer

s:H

ydra

te Is

omer

s

Hyd

rate

Isom

ers:

hav

ing

wat

er a

s ei

ther

a

ligan

dor

an

adde

d pa

rt o

f the

cry

stal

str

uctu

re

Isom

eris

m –

Con

stitu

tiona

l Iso

mer

s:Io

niza

tion

Isom

eris

m

Ioni

zatio

n Is

omer

s: E

xcha

nge

of io

nsbe

twee

n in

side

and

out

side

coo

rdin

atio

n sp

here

Isom

eris

m –

Con

stitu

tiona

l Iso

mer

s:C

oord

inat

ion

Isom

eris

m

Coo

rdin

atio

n Is

omer

s: re

quire

at l

east

two

met

al

Isom

eris

m –

Con

stitu

tiona

l Iso

mer

s:Li

nkag

e (a

mbi

dent

ate)

Isom

eris

m

Link

age

Isom

ers:

Com

poun

ds c

onta

inin

g am

bide

ntat

elig

and

thio

cyan

ate

nitr

ite

thio

cyan

ois

othi

ocya

no

nitr

oni

trito

Sep

arat

ion

Frac

tiona

l Cry

stal

izat

ion

–pa

ckin

g, s

olub

ility

, siz

e, c

harg

e

Chi

ralI

som

ers

Res

olut

ion

–ch

iralc

ount

erio

ns

Iden

tific

atio

n

X-r

ay c

ryst

allo

grap

hy

Opt

ical

rota

tory

disp

ersi

on (O

RD

)

Circ

ular

dic

hroi

sm(C

D)

Isom

eris

m –

Sepa

ratio

n an

d Id

entif

icat

ion

of Is

omer

s

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

s

Kno

wn

up to

16

CN

8≤

Pen

tago

nal b

ipyr

amid

, Cap

ped

trigo

nal

pris

m, C

appe

d oc

tahe

dron

7

Oct

ahed

ron,

Trig

onal

pros

m6

Trig

onal

bipy

ram

id, S

quar

e py

ram

id5

Tetr

ahed

ron,

Squ

are-

plan

e4

Trig

onal

-pla

ne3

Line

ar2

Rar

e1

Geo

met

ries

CN

Fact

ors

for S

truct

ures

1.N

umbe

r of B

onds

Bon

d fo

rmat

ion

is u

sual

ly

exot

herm

ic.

So

stab

ility

2.V

SE

PR

3.O

ccup

ancy

of d

orb

itals

Squ

are-

plan

ar v

sTe

trahe

dral

4.S

teric

Effe

cts

5.C

ryst

al P

acki

ng E

ffect

sC

ryst

allin

e La

ttice

vs

Sol

utio

n

Wha

t is

com

mon

thin

g?W

hich

one

is a

dom

inan

t fac

tor?

Stru

ctur

es v

sPr

oper

ties.

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

s

Oxi

datio

n St

ates

of T

rans

ition

Met

als

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

1,2

, and

3

CN

= 1

, Rar

e

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

1,2

, and

3

CN

= 2

, Rar

e, L

inea

r (D

∞h)

Mos

tly d

10m

etal

s, A

g(I),

Cu(

I), A

u(I),

Hg(

II)d5 ,

d6 , d7

Exa

mpl

es o

f CN

= 2

Larg

e Li

gand

sca

n in

duce

a li

near

arr

ange

men

t

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

1,2

, and

3

CN

= 3

, Rar

e, T

rigon

alpl

anar

(D3h

)M

ostly

d10

, PP

h 3, N

(SiM

e 3) 2

, B

ulky

eno

ugh,

Ste

ricef

fect

vs

Elec

troi

cst

ruct

ure

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

4

CN

= 4

, Tet

rahe

dral

(Td)

Squ

re-p

lana

r(D

4h)

Tetr

ahed

ral (

T d) ;

ver

y c

omm

on,

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

4

CN

= 4

, Tet

rahe

dral

(Td)

Squ

re-p

lana

r(D

4h)

Squr

e-pl

anar

(D4h

) ; m

ostly

d8

(Pd(

II), P

t(II),

Ni(I

I), A

g(III

), Ir(

I) R

h(I))

Tetr

ahed

ral v

sSq

uare

-pla

nar

Cou

nter

ion,

Cry

stal

Pac

king

Cl

Cu

Cl

ClC

l2C

s

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

4

CN

= 4

, Tet

rahe

dral

(Td)

Squ

re-p

lana

r(D

4h)

Squr

e-pl

anar

(D4h

) ; m

ostly

d8

(Pd(

II), P

t(II),

Ni(I

I), A

g(III

), Ir(

I) R

h(I))

Tetr

ahed

ral v

sSq

uare

-pla

nar

Cou

nter

ion,

Cry

stal

Pac

king

∆E

is n

ot b

ig.

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

5

CN

= 5

, Trig

onal

bipy

ram

id(D

3h),

Squa

re p

yram

id (C

4v)

Flux

iona

l beh

avio

r.

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

6

CN

= 6

, Oct

ahed

ral (

Oh)

mos

t com

mon

Oh

toD

4h

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

6

CN

= 6

, Oct

ahed

ral (

Oh)

to T

rigon

alPr

ism

(D3h

)

Usu

ally

with

thre

e bi

dent

ate

ligan

ds

πIn

tera

ctio

ns b

etw

een

adja

cent

sul

fur a

tom

s

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

7

CN

= 7

, Pen

tago

nal b

ipyr

amid

(Oh)

, Cap

ped

trig

onal

pris

m, C

appe

d oc

tahe

dron

Cap

ped

trigo

nalp

rism

Pen

tago

nal b

ipyr

amid

Cap

ped

octa

hedr

on

Diff

eren

t cou

nter

ion,

ste

ricre

quirm

ent

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N =

8

CN

= 8

, Squ

are

antip

rism

, Dod

ecah

edro

n

Eigh

t coo

rdin

atio

n is

rare

in

the

first

row

tran

sitio

n m

etal

s

Why

?

Cen

tral

ion

mus

t be

larg

e in

ord

er to

ac

com

mod

ate

eigh

t-co

ordi

natio

n

Squ

are

antip

rism

Dod

ecah

edro

n

Com

pres

sed

Squ

are

antip

rism

Coo

rdin

atio

n N

umbe

rs a

nd S

truc

ture

sC

N ≥

8

CN

≥8,

kno

wn

up to

16,

not

com

mon

Mul

timet

allic

Com

pexe

s

With

out d

irect

M-M

bon

d

With

dire

ct M

-M b

ond