National Technical University of Ukraine 1

‘Igor Sikorsky Kiev Polytechnic Institute’

Organometallic Chemistry
(Structure, Reactivity, and Mechanisms)

Hydroformylation
(Oxo-process)
Andrey O. Kushko, Ph.D.,
Senior Lecturer

Kiev-KPI-2023
Catalytic Hydroformylation: Introduction 2

What is Hydroformylation?

Produces aldehyde from alkene via addition of

a CO and H2 to a alkene:

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

 3
Thermodynamics of
hydroformylation
and hydrogenation
of propene
 4
Roelen (Ruhrchemie AG) hydroformylation

“Normal” “Iso-”
linear product branched product

Otto Roelen (1897-1993)

(Photo: LVR-Industriemuseum, collection
Ruhrchemie).

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

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R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

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Products Derived from Aldehydes

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

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Hydroformylation: from discovery to the modern trends 8
 Typical Laboratory-Scale Setup 9

Showing the autoclave unit (A), from which

RTAP (room temperature/ambient pressure)
hydroformylation apparatus
Seiche, W.; Schuschkowski, A.; Breit, B. Adv. Synth. Catal.
2005, 347, 1488.
the reaction solution is transferred to the IR
transmission cell (C) through a capillary
process with the help of a microgear pump (P)
and is recirculated. 103 A modified version of
a Bruker Tensor 27 FTIR spectrometer (S) is
placed inside the same hood
 10
Catalyst: HCo(CO)4 (Cobalt Tetracarbonyl Hydride)

CO OC CO
Structure of
Precatalys Co2(CO)8 = (OC)4Co Co(CO)4 = OC Co Co CO
OC CO CO

Catalyst Formation:
O
C H2 (OC)4Co Co(CO)4
(OC)3Co Co(CO)3 (OC)4Co Co(CO)4 2 H Co(CO)4
H H
C
O -bond metathesis

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

Catalyst: HCo(CO)4 (Cobalt Tetracarbonyl Hydride) 11

• oldest homogeneous catalysis process still in use;

• total H2/CO (ratio= 1:1), pressures of 200- 300 bar and 110- 180 °C;
• ratio of linear to branched aldehyde: ca. 4 to 1;
• decomposed to metallic Co at high temperature and low CO pressure
R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.
 12
Cobalt Tetracarbonyl Hydride: Properties

HCo(CO)4 adopts trigonal bipyramidal structure with the equatorial CO ligands

slightly bent out of the equatorial plane. The hydride ligand occupies one of the
axial positions, thus the symmetry of the molecule is C3v. The Co–CO and Co–H
bond distances were determined by gas-phase electron diffraction to be 1.764
and 1.556 Å, respectively. Assuming the presence of a formal hydride ion,
the oxidation state of cobalt in this compound is +1.
But unlike some other transition-metal hydride complexes, HCo(CO)4 is highly
acidic, with a pKa of 8.5. It readily undergoes substitution by tertiary
phosphines and other Lewis-bases. For example, triphenylphosphine gives
HCo(CO)3PPh3 and HCo(CO)2(PPh3)2. These derivatives are more stable than
HCo(CO)4 and are used industrially to improve catalyst selectivity in
hydroformylation.[8] These derivatives are generally less acidic than HCo(CO)4.

B. F. G. Johnson, R. E. Benfield in G. L. Geoffroy (ed.): Topics in Inorganic Stereochemistry, Wiley, New York
1981, pp. 253 – 335.
 13
Mechanism of Hydroformylation Catalyzed by HCo(CO)4

Heck and Breslow JACS 1961 (83) 4023. Sommer JACS 1969 (91) 7051.
 Mechanism of Hydroformylation Catalyzed by HCo(CO)4 14

Heck and Breslow JACS 1961

(83) 4023. Sommer JACS 1969
(91) 7051.
 15

Free Energy
Surface of the
Catalytic Cycle

Angew. Chem. 2012, 124, 11195 –11200.

 16
Hydroformylation of Internal Alkenes
Under the reaction conditions HCo(CO)4 is an effective isomerization catalyst. The linear-to-branched
ratio obtained is the same for terminal and internal alkenes. This means that alkene addition or insertion
is definitely not rate-determining in this system. 1-Alkenes, but also internal alkenes, are rapidly
isomerised to the thermodynamic mixture of terminal and internal alkenes.

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

 17
Phosphine Modified Cobalt Catalysts: the Shell Process

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

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Preparation of Modified Cobalt Precatalyst

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

 19
A Ligand Reported by Shell for Co Hydroformylation

Slaugh, L. H.; Mullineaux, R. D. U.S. Pat. 3,239,569 and 3,239,570, 1966 (to Shell); Chem. Abstr. 1964, 64, 15745 and 19420.
 20
Shell Hydroformylation: Regioselectivity

Slaugh, L. H.; Mullineaux, R. D. J. Organomet. Chem. 1968, 13, 469.

 21
Hydroformylation of Internal Alkenes Catalyzed by
HCo(CO)3(PR3)

Hershman, A.; Craddock, J. H. Ind. Eng. Chem. Prod. Res. Develop. 1968, 7,226.
 22
Examples of Complexes involved in Cobalt
Hydroformylation

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

 23
Lim Ligands developed by Sasol; Position R Group not
defined

Steynberg, J. P.; Govender, K.; Steynberg, P. J. WO Patent, 2002014248, 2002.


General Types of Ligands
Order of activity in hydroformylation
was found with corresponding Rh
catalysts
24
Classification of trivalent P-ligands
based on the nature of the α-atom
next to the phosphorus.

Carlock, J. T. Tetrahedron, 1984, 40, 185. van der

Veen, L. A.; Keeven, P. K.; Kamer, P. C. J.; van
Leeuwen, P. W. N. M. Chem. Commun., 2000, 333.
 25
-Acceptor and σ-Donor properties of P-Ligands with
different P−X (X = C, O, N) Bonds

Trzeciak, A. M.; Glowiak, T.; Grzybek, R.; Ziółkowski, J. J. J. Chem. Soc., Dalton Trans. 1997, 1831.
 26
Commonly used Models for Steric Characterization of
Phosphorus Ligands

The concept of the natural bite angle,

α, has been especially developed for
hydroformylation in order to get some
insights into the relationship between
activity and regioselectivity of
homogeneous rhodium catalysts

Tolman, C. A. Chem. Rev. 1977, 77, 313. Allman, T.; Goel, R. G. Can. J. Chem. 1982, 60, 716. Tolman, C. A. J. Am. Chem.
Soc. 1970, 92, 2956. Casey, C. P.; Whiteker, G. T. Isr. J. Chem. 1990, 30, 299. Goertz, W.; Kamer, P. C. J.; van Leeuwen,
P. W. N.; Vogt, D. J. Chem. Soc., Chem. Commun. 1997, 1521. Dierkes, P.; van Leeuwen, P. W. N. M. Dalton Trans. 1999,
1519. Achord, P. D.; Kiprof, P.; Barker, B. THEOCHEM 2008, 849, 103. Birkholz, M.-N.; Freixa, Z.; van Leeuwen, P. W. N. M.
Chem. Soc. Rev. 2009, 38, 1099.
 27
Catalysts Containing Wide-Bite-Angle
Bisphosphines

Casey, C. P.; Whiteker, G. T.; Melville, M. G.; Petrovich, L. M.; Gavney, J. A.; Powell, D. R. J. Am. Chem.
Soc. 1992, 114, 5535.
 28
Bisphoshine Ligands tested for the Generation of
Regioselective Hydroformylation Catalysts

Sanger, A. R.; Schallig, L. R. J. Mol. Catal. 1977, 3, 101. Sanger, A. R. J. Mol. Catal. 1978, 3, 221. Pittman, C. U.;
Hirao, A. J. Org. Chem. 1978, 43, 640.
 29
Relationship between several Ligand Bite Angles and n:i
Selectivity for Propene Hydroformylation

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

 30
Hydroformylation Catalytic Cycle with Monophosphine
Rhodium Catalyst

J. Pospech, I. Fleischer, R. Franke, S.

Buchholz, M. Beller, Angew. Chem. Int. Ed.
2013, 52, 2852 – 2872.
 31
Alternative Metals for Homogeneous Catalyzed
Hydroformylation Reactions
The typical catalysts for hydroformylation of olefins are homogeneous complexes of the type
[HM(CO)xLy ], where L can be further CO or an organic ligand. A generally accepted series of
the activities of the unmodified metal is as follows:

To date, only rhodium and cobalt are used in industrial

practice!
J. Pospech, I. Fleischer, R. Franke, S. Buchholz, M. Beller, Angew. Chem. Int. Ed. 2013, 52, 2852 – 2872. Pruchnik, F. P.
Organometallic Chemistry of Transition Elements; Plenum Press: New York, 1990; p 691.
 32
Process Parameters for Several Hydroformylation
Processes
Process Parameters Cobalt Cobalt+Phosphine Rhodium+Phosphine
Temperature (oC) 140-180 160-200 90-110
Pressure (atm) 200-300 50-100 10-20
Alkane Formation Low Considerable Low
Main Product Aldehyde Alcohol Aldehyde
Selectivity (%) to n- 75-80 85-90 92-95
butyraldehyde
Isolation of Catalyst Difficult; HCo(CO)4 Less difficult Less difficult; water-
is volatile soluble phosphine a
major advancement

R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675−5732.

 33
General Method for the Preparation
of a P-Modified Rh precatalyst

[Rh(acac)(CO)2] + Px + H2 + CO [HRh(CO)3P] + [HRh(CO)2P2] + ...

- Hacac

H3C
C O Dwyer, C.; Assumption, H.; Coetzee, J.; Crause, C.; Damoense, L.; Kirk,
M. Coord. Chem. Rev. 2004, 248, 653. Damoense, L.; Datt, M; Green,
M.; Steenkamp, C. Chem. Rev. 2012, 112, 5675−5732 5722. Kamer, P.
C OH C. J.; van Rooy, A.; Schoemaker, G. C.; van Leeuwen, P. W. N. M.
H3C Coord. Chem. Rev. 2004, 248, 2409. Lazzaroni, R.; Settambolo, R.;
acac Alagona, G.; Gio, C. Coord. Chem. Rev. 2010, 254, 696. Kubis, C.;
Ludwig, R.; Sawall, M.; Neymeyr, K.; Börner, A.; Wiese, K.-D.; Hess, D.;
Franke, R.; Selent, D. Chem. Cat. Chem. 2010, 2, 287.
 34
Formation of Different P−Rh Complexes in Dependence on
the Concentration of CO and P-Ligand
Pruett and coworkers at Union Carbide
found that the combination of rhodium
precursors and excess PPh3 created an
active, selective, and stable system that
catalyzed hydroformylation with 5-10
atm of CO and H2 at 90 °C. This system
was developed into a commercial
hydroformylation process in the early
1970s. Excess PPh3 was used to
replenish PPh3 that is lost by
degradation through several different
pathways and to favor formation of
Praett, R. L.; Smith, J. A. J. Org. Chem. 1969, 34, 327. van Leeuwen, P. W. M. HRh(CO)2(PPh3)2 over less selective
N.; Casey, C. P.; Whiteker, G. T. In Rhodium Catalyzed Hydroformylation; van rhodium complexes containing fewer
Leeuwen, P. W. N. M., Claver, C., Eds.; Kluwer: Dordrecht, The Netherlands , PPh3 ligands. Hydroformylation
2000; Vol. 22, Chapter 4.
reactions conducted with higher
concentrations of PPh3 occur more
slowly, but with higher mi selectivity.
 35
Relative Rates and n:i Ratios for Reaction of Substituted
Alkenes

VanRooy, A.; de Bruijn, J. N. H.; Roobeek, K. F.; Kamer, P. C. J.; van Leeuwen, P. J. Organomet. Chem.
1996 , 507, 69 .
 36
Hydroformylation Catalyzed by Rhodium Complexes
of Phosphites

Kamer, P. C. J.; Reek, J. N. H.; van Leeuwen, P. W. N. M. In Rhodium Catalyzed Hydroformylation-,

van Leeuwen, P. W. N. M., Claver, C., Eds.; Kluwer: Dordrecht, The Netherlands , 2000; Vol. 22, Chapter 3.
 37
Rhodium-Catalyzed Hydroformylation of Internal Alkenes

van der Veen, L. A.; Kamer, P. C. J.; van Leeuwen, P. Angew.

Chem. Int. Ed., 1999, 38, 336.
 38
Rhodium-Catalyzed Hydroformylation of Functionalized
Alkenes

Leighton, J. L.; O'Neil, D. N. J. Am. Chem. Soc. 1997, 119,

11118. Sarraf, S. T.; Leighton, J. L. Tetrahedron Lett. 1998,
39, 6423. Botteghi, C.; Soccolini, F. Synthesis, 1985, 592.
Polo, A.; Claver, C.; Cas tillon, S.; Ruiz, A.; Bayon, J. C.;
Real, J.; Mealli, C.; Masi, D. Organometallics, 1992, 11,
3525.
 39

One-Pot Rhodium-Catalyzed Hydroxymethylation

HAL Id:hal-03820164 https://hal.archives-ouvertes.fr/hal-03820164, Submitted on18 Oct 2022

 Reactions of many olefins containing electron- 40

withdrawing functional groups at the C=C bond react to

form branched substitution products

Castillon, S.; Fernandez, E. In Rhodium

Catalyzed Hydroformylation; van Leeuwen, P.
W. N. M., Claver, C., Eds.; Kluwer: Dordrecht,
The Netherlands , 2000; Vol. 22, p 284. Fell, B.;
Barl, M. J. Mol. Catal. 1977, 2, 301. Abatjoglou,
A. G.; Bryant, D. R.; Desposito, L. C. J. Mol.
Catal. 1983, 18, 381. Becker, Y.; Eisenstadt, A.;
Stille, J. K. J. Org. Chem. 1980, 45, 2145.
Delogu, G.; Faedda, G.; Gladiali, S. J.
Organomet. Chem. 1984, 268, 167. Ojima , I.
Chem. Rev. 1988, 88, 1011. Fuchikami, T.;
Ojima , I. J. Am. Chem. Soc. 1982, 104, 3527.
Crameri, Y.; Ochsner, P. A.; Schude l, P.
European Patent Appl. EP52775, 1982.
Lazzaroni, R.; Settambolo, R.; Uccellobarretta,
G. Organometallics, 1995, 14, 4644.
 41
Understanding a Hydroformylation
Catalyst that Produces Branched
Aldehydes from Alkyl Alkenes

P. Dingwall, J.́ A. Fuentes, L. Crawford, A. M. Z. Slawin, M.

Bühl, M. L. Clarke, J. Am. Chem. Soc. 2017, 139,
15921−15932
 42

BOBPHOS Parent Ligands and Selected Examples of

High-Branched Selectivity

P. Dingwall, J.́ A. Fuentes, L. Crawford, A. M. Z. Slawin, M.

Bühl, M. L. Clarke, J. Am. Chem. Soc. 2017, 139,
15921−15932
 43
Ruthenium-Catalyzed Hydroformylation

D. Evans, J. A. Osborn, F. H. Jardine, G. Wilkinson, Nature, 1965, 208, 1203 – 1204.

G. Sss-Fink, J. Organomet. Chem. 1980, 193, C20 – C22; B. F. G. Johnson, J. Lewis, P. R. Raithby, G. Suss,
J. Chem. Soc. Dalton Trans. 1979, 1356 – 1361.
 44
Proposed catalytic cycle for
[Ru(CO)3(PPh3)2]-catalyzed
hydroformylation

R. A. Sanchez-Delgado, J. S. Bradley, G.
Wilkinson, J. Chem. Soc. Dalton Trans.
1976, 399 – 404.
 45
Ru-Catalyzed Hydroformylation of Propylene in DMF
and Diglyme

G. Sss-Fink, J. Organomet. Chem. 1980, 193, C20 – C22; B. F. G. Johnson, J. Lewis, P. R. Raithby, G. Suss, J. Chem.
Soc. Dalton Trans. 1979, 1356 – 1361. G. Sss-Fink, G. F. Schmidt, J. Mol. Catal. 1987, 42, 361 – 366.
 46

Proposed catalytic cycle for

the hydroformylation of
ethene by the cluster
anion [Ru3H(CO)11]-

G. Sss-Fink, G. Herrmann, J. Chem.

Soc. Chem. Commun. 1985, 735 – 737.
 47

Hydroformylation:
Asymmetric and
Heterogeneous
48