Organometallic Chemistry

Raja Angamuthu
Department of Chemistry
Indian Institute of Technology Kanpur
Ø 7 Steps in Mastering Organometallics

ü Periodic Table
ü Ligands
ü Electron Count (18e rule)
ü Oxidative Addition
ü Reductive Elimination
ü b-Hydride Transfer/Elimination
ü Migratory Insertion
Ø Periodic Table

Sc Ti V Cr Mn Fe Co Ni Cu Zn

Y Zr Nb Mo Tc Ru Rh Pd Ag Cd

La Hf Ta W Re Os Ir Pt Au Hg

Early Middle Late

d1 d2 d3 d4 d5 d6 d7 d8 d9 d10
Sc2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+

Y2+ Zr2+ Nb2+ Mo2+ Tc2+ Ru2+ Rh2+ Pd2+ Ag2+ Cd2+

La2+ Hf2+ Ta2+ W2+ Re2+ Os2+ Ir2+ Pt2+ Au2+ Hg2+
Ø Ligands

ü Nature of the ligands

ü Charge of the ligands

ü Binding modes

ü Number of electrons donated

R3
P O
C
H Curious to know?
H Ø IR
OC W
Ø NMR
M H Ø X-ray Diffraction
H OC P Ø Neutron Diffraction
R3

W(η2-H2)(CO)3[P(i-Pr)3]2

J. Am. Chem. Soc. 1984, 106, 2, 451–452; J. Chem. Educ. 1996, 73, 10, 988
Ø Hydride: Anionic 2e donor

H
Ph 3P
+2,18
Rh PPh 3
Ph 3P S S
C Fe Fe
O Cp* Cp*
H

Curious to know?
Ø What is Cp*

J. Chem. Soc. A, 1968, 3133-3142; Inorg. Chem. 2015, 54, 21, 10243–10249
Ø Hydride: Anionic 2e donor
P
R R 2+

H R P P R
H
R R
P H P Cu Cu
R P H P R
P H
P Cu
H H P P
R R R R

P
[(R3P)Cu(μ3-H)]6 [Cu3(dcpm)3(μ3-H)]2+
Stryker’s reagent

J. Am. Chem. Soc. 1989, 111, 3472–3473; J. Am. Chem. Soc. 2005, 127, 4562–4563
Ø Hydride: Anionic 2e donor

Ru Co

Ru Co
Ru H Ru Co H Co
Ru Co

Ru Co
[HRu6(CO)18]− [HCo6(CO)15]−

J. Chem. Soc., Chem. Commun., 1976, 945-946; Angew. Chem. Int. Ed. 1998, 37, 2193–2197
Ø Halides: anionic 2e, 4e or 6e donor

PPh 3

Ph 3P I Cu
Ph 3P
Cu I
Cu I

I Cu

PPh 3

J. Am. Chem. Soc. 76, 4281–4284; Inorg. Synth., 21, 74–78; Dalton Trans., 2019,48, 7899-7909
Ø H2O, ROH, RSH, R2O, R2S:
H H H H
O S

M M

R
R H R H
O S
S
R M
M M
M
Cl CO
S S Cl
Ru Ru
R R R R Cl S
S
O S CO Cl

M M
Neutral 2e and 4e donors
Neutral 2e donors Dalton Trans., 2010, 39, 5713–5720
Ø HO – and HS :
–

PCy 3 H
OC H CO CO H
Ru Ru Cy3P OC
H O PCy 3
(tBu) 2P Ni P(tBu) 2 PCy 3 Cl Ru Ru PCy 3
H
H
OH O H
2e donor 4e donor O
OC
Cl H
H Ru Ru
SH Cp* S Rh H O
Ti CO PCy 3
SH Rh S Cp* Cy3P H
H 6e donor
Cl
2e donor 4e donor Curious to know about (µ3-SH) ???
Chem. Eur. J. 2012, 18, 6915 – 6927; Organometallics 1985, 4, 524-528;
Organometallics 2006, 25, 1047–1051; Organometallics 1997, 16, 151–154
Ø RO – and RS :
–
P(tBu) 2
O S
O
Pd OCH3 Ti Ti
O
Fe(CO) 3
(OC) 3Fe
P(tBu) 2
Fe(CO) 3
2e donor 4e donor 6e donor H
R
(OC) 3Mn S
R
S S Mn(CO) 3
Ti R S Mn(CO) 3
S S S
Fe Fe (OC) 3Mn S
Cp* Cp*
H R
2e donor 4e donor Curious to know about (µ3-OR) ???

J. Am. Chem. Soc. 2011, 133, 17713–17726; Inorg. Chem. 2017, 56, 3324−3334; Inorg. Chem. 2015, 54, 21,
10243–10249; Inorg. Chim. Acta 2018, 480, 47–53; Dalton Trans., 2016, 45, 13222-13233