Organic chemistry Unit -II

A) ORGANOMETALLIC COMPOUNDS
Organic Compounds in which a metal atom is linked directly to a carbon atom are called as Organometallic Compounds. A large number of metals e.g. Lithium (Li), Sodium ( a), !agnesium (!g), "inc ("n), !ercury (#g), Lead ($b), Cadmium (Cd) etc. form such compounds. %he organic part is generally an Alkyl, Alkenyl, Alkynyl or an Aryl group. !ethyllithium *thylmagnesium n+)utlylithium ,iethylmercury %etraethyllead $henyllithium ,imethylcadmium ,iethyl/inc

8enerally, the larger the ionic character of carbon+ metal bond, more reacti0e is the organometallic compound.

O,-.NOM.-NE%I/M COM#O/N0%
Organometallic #alides are e9tremely important reagents in synthetic organic chemistry. %hese are commonly known as -rignard ,eagents after the name of the disco0erer, Victor Grignard recei0ed the obel pri/e in chemistry in :;:' for this disco0ery. %he general formula of 8rignard reagents in <+!g+= Ar+!g+= where < is any alkyl group Ar is any aryl group.

Example: C#&Li C'#(!g)r C#&C#'C#'C#'Li (C'#()'#g (C'#()-$b C.#(Li (C#&)'Cd (C'#()'"n

#,E#.,.1ION:
5n the Laboratory, 8rignard <eagents are prepared by the action of an Alkyl or an Aryl #alide ($referably )romide or 5odide) on magnesium metal (turnings) in ,ry *ther.
,ry *ther

-eneral: <= Examples:

,ry *ther

!g

<!g=

.l2yl 3alide

%he Carbon+!etal bond in Organometallic compounds differs widely 0arying from ionic to co0alent. Example:

i) ii)

C#&= C'#()r

3 3

!g
,ry *ther

C#&!g= C'#()r !g=

Met3yl iodine

!g

Et3yl $romide

gely cti0e !ost 6

Ionic (M = Na or K) iii) b2co/ of weak bonding of carbon )r 3 !g *lectro3 Alkali !etals 4

,ry *ther

!g)r
#3enylmagnesium (romide

(romo$en4ene

character

b2co/

of

partial

37+

i!)
%#>

Cl 3 !g Co!alent (M = "g #$ %n) b2co/ of strong bond 4 Co0alent )ond6

Order o& reacti!ity' Ionic (ond
C3loro$en4ene #3enylmagnesium

!gCl

acti0e

C3loride
) #artial *+' ) Co!alent (ond.

%#>

!) C#' ? C#@Cl 3 !g
5inyl c3loride

C#' ? C# @!gCl
5inylmagnesium

c3loride

)eside *ther, %etrahydrofuran (%#>), ,io9ane, ,imetho9yethane (,!*) or ,imethyl ether of ,iethylene glycol (diglyme), tertiary amines etc. can also be used as sol0ents. %#> (C#')-O

with the formation of a small amount of magnesium halide and then proceeds by a free radical mech. <@= 3 !g 3 =@< !g=' 3 !g <= 3 !g= . . < 3 !g= <@< 3 !g=' . '!g= . < 3 !g=' <!g=

,!* C#&+O+C#'+C#'+O+C#& >urther, it has been found that for a gi0en alkyl group, the ease of formation of 8rignard reagents is of the orderA iodide B bromide B chloride. %he alkyl or arylmagnesium fluodies are, howe0er, unknown. >or a gi0en halogen atom, the order of reacti0ity is C#&= B C'#(= B C&#C=DDetc
(!ore reacti0e) (Less reacti0e)

%his mech. also elegantly (simply) e9plains the initiating effect of iodine which may be ascribed (belong) to the formation of magnesium iodide from magnesium and iodine.

i.e. in the formation of 8rignard reagents becomes increasingly difficult with increase in the number of carbon atoms in the alkyl group. %he use of tertiary alkyl iodides is a0oided since they readily lose a molecule of hydrogen iodide to form an alkene. %ertiary alkyl chlorides may then be used.

%1,/C1/,E O6 -,I-N.,0 ,E.-EN1: %he structure of 8rignard reagent has not been finally settled so far. %he recent research has shown that the actual structure 0aries with particular 8rignard reagent and the sol0ent used for its preparation. 8rignard and )laise (:;E:) obser0ed that e0aporation of ethereal solution of 8rignard reagent resulted in a white solid ha0ing the composition <!g= . '(C'#()'O. %hey suggested that ether molecules were present as Fether of crystalli/ation.2 =+ray analysis of these di+etherates suggests that the four groups are arranged tetrahedrally as shown in formula (:)

#rocedure &or -rignard ,eagents: Alkyl or aryl #alide is added slowly to a perfectly clean and dry flask containing dry magnesium turnings co0ered by a layer of absolutely dry ether or %#>. %he reaction mi9ture is warned a little when an e9othermic reaction should soon start. 5f the reaction does not start within fi0e minutes, a few crystals of iodine are added and the reaction mi9ture is warned a little. A 0igorous reaction soon sets in and magnesium gradually dissol0es forming a cloudy solution of the 8rignard reagent.

Mec3anism: %he mech. Of the formation of 8rignard reagent is still not certain (specific). According to 8omberg and )eckmann (:;&E) the reaction commences (start, begin)

%hus, formula (I)suggests that ether does not merely provide a medium for the reaction but it also helps to dissolve the Grignard reagents formed due to solvation by ether molecule. %his is suppoted by the obser0ation that 8rignard reagents can be prepared e0en in ben/ene solution in presence of a tertiary amine which coordinates with magnesium like ether and thus dissol0es it. >uther, formula (55) shows the 8rignard reagents in the monomeric form but physical studies ha0e re0ealed (disclose) that 8rignard reagents e9ist as a :G: comple9 of a dialkyl or diarymagnesium and magnesium halide coordinated with molecules of ether. %hese two species are held together by halogen bridges as shown in formula (55)