UNIVERSITY OF DAR ES SALAM

CH 379: ORGANOMETALLIC CHEMISTRY

ORGANOMANGANESE CHEMISTRY
MDOGELWA ASHERY (2021-04-06736)
COURSE COODINATOR: DR. NDOILE
TOPIC OUTLINE
 INTRODUCTION
 SYNTHESIS OF ORGANOMANGANESE
 REACTIONS
 APPLICATION
 C0NCLUSION
INTRODUCTION
MANGANESE

• Is a silvery-grey transition metal with the chemical symbol of Mn

and atomic number 25.
• It is d-block element found in group 7 and period 4 in periodic
table.
• Electronic configuration [Ar]3d54s2
• As other transition metals, manganese has various oxidation state
which are +2, +3, +4 ,+6 and +7 where the most stable is +2.
ORGANOMANGANESE
• Is the organometallic compound with carbon to manganese bond (C-Mn). They have
potential as chemical reagents and catalyst in different chemical reactions .
• The first organomanganese compounds to be synthesized was in 1937 by Gilman and
Bailee by reaction of phenylithium with manganese (ii) iodide to form phenyl manganese
iodide and diphenyl manganese

Li THF MnI

+ MnI2 + LiI
 SELECTED EXAMPLES OF ORGANOMANGNESE COMPOUNDS

MnI

Mn

Methyl cyclopentadienyl phenyl manganese iodide

Manganese tricarbonyl Bis(cyclopentadienyl) manganese

Mn N CH
N
(tBu)2P Mn P(tBu)2
N OC
CO
X

SYNTHESIS OF ORGANOMANGANESE COMPOUNDS

Earlier, the most common method of preparation of organomanganese compounds was
• Transmetalation from corresponding organolithium or organomagnesium

RM + MnX2→ 2RMnX + MX

RLi + MnCl2→ 2RMnCl + LiCl

Also organomanganate (organomanganese with higher oxidation state) can be prepared in

this method in excess organolithium or organomagnesium

3RM + MnX2→ R3MnX + 2MX

4RM + MnX2→ R4MnX2+ 2MX

 Oxidactive addition of organic halide to activated manganese i.e direct
insertion of Mn to R-X bond

R-X + Mn* R-MnX

Since unactivated manganese is less active due to formation of layer of
oxide. Hence needs to be activated and highly activated Mn* (Rieke
manganese) is obtained by reduction of Mn2+

MnBr2 + Li/Naphthalene+ THF Mn*

 Manganese- halogen exchange reaction between organic halide and
tetralkylmanganate leads to the formation of organomanganese
halides

R-X+ Bu4MnLi R-MnX

Manganocene
• Is a organomanganese compound with the chemical formula [Mn(C5H5)n]

• It is a thermochromic solid that degrades rapidly in air.

Mn

Bis(cyclopentadienyl) manganese

• As other metallocene compounds, manganocene is applied to the

polymerization reaction of ethylene to form polyethylene .It is prepared in
the manner common to other metallocene that is ;

MnCl2 + 2CpNa Cp2Mn + 2NaCl

REACTIONS OF ORGANOMANGANESE
• Due to comparable electronegativity of manganese (EN 1.55) with that of
magnesium (EN 1.31) the reactivity of organomanganese compounds can be
compared to that of organomagnesium.
• Organomanganese compounds can undergo the following reactions;
 Reaction with aldehyde and ketone to form secondary and tertiary alcohol respectively

O 1.R1MnX OH

R H 2.H , H2O R R1

O 1.R1MnX OH
R1
R R2 2.H , H2O R R2

 Reaction with carbon dioxide gas to form carboxylic acid

H3O O
R MnCl + CO2 R OH
 Cross coupling reaction
Cross coupling reaction with organomanganese compounds.
O O
Mn
+ MnCl2
THF
Cl
(75%)

O O
MeMnCl
+ MnCl2
Ph Cl (low temperature)Ph Me

Iron-Catalyzed Cross-Coupling of Organomanganese Compounds

The iron-catalyzed alkenylation of organomanganese reagents is efficiently performed in
THF at room temperature. The reaction is very chemoselective; thus, even a keto group
is tolerated
O O
MnCl
Cl
THF,r.t,1hr
3% Fe(acac)3
APPLICATION OF ORGANOMANGANESE COMPOUNDS

Organomanganese compounds have been useful reagents in the followings;

 Organic synthesis chemistry
 As a catalyst
 Functionalization reactions
CONCLUSION

Organomanganese compounds can be used as soft Grignard reagents, for instance, to

perform chemoselective 1,2- addition, copper-catalyzed conjugated addition, acylation,
and carbonation reaction. On the other hand, these reagents can also behave like
transition metal derivatives, highlighted by the mild and efficient manganese-catalyzed
homo- and hetero coupling reactions
 REFFERENCES
 Robert J. Morris ,GregoryS. Girolami, 1991 Organometallics “high valent organomanganese
chemistry.1 synthesis and characterization
 Sanshiro Komiya. M Hurano 1997 Synthesis of organometallic compounds: A practical guide.
 Layfield, Richard A. "Manganese(II): The Black Sheep of the Organometallic Family".
Chem. Soc. Rev. 1098-1107.
 Recent Synthetic Applications of Manganese in Organic Synthesis José M.
Concellón,
 Humberto Rodríguez-Solla, Vicente del Amo Chemistry - A European Journal Volume
14 Issue 33, Pages 10184 - 10191
 Transition metal bicyclo[2.2.1]hept-1-yls Barton K. Bower, Howard G. Tennent
J. Am. Chem. Soc., 1972, 94 (7), pp 2512–2514
THANK YOU!