Synthesis, spectroscopy, and hydroformylation activity of sterically demanding, phosphite-modified cobalt catalysts

Reinout Meijboom; Marco Haumann; Andreas Roodt; Llewellyn Damoense

doi:10.1002/hlca.200590047

Synthesis, spectroscopy, and hydroformylation activity of sterically demanding, phosphite-modified cobalt catalysts

Reinout Meijboom, Marco Haumann, Andreas Roodt, Llewellyn Damoense

Chemical Sciences

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

The dinuclear complex [Co₂(CO)₆{P(O-2,4-t-Bu ₂C₆H₃)₃}₂] (6) has been synthesised and fully characterised. X-Ray crystal-structure analysis revealed a trans-diaxial geometry, no bridging carbonyls, and Co-Co and Co-P bond lengths of 2.706(5) and 2.134(4) Å, respectively. The hydroformylation of pent-1-ene in the presence of 6 was studied at 120-180° at pressures between 20 and 80 bar Syngas. High-pressure (HP) spectroscopy (IR, NMR) was used to detect potential hydride intermediates. HP-IR Studies revealed the formation of [CoH(CO)₃{P(O-2,4-t-Bu₂C₆H₃) ₃}] (2) at ca. 105°, with no significant amount of [CoH(CO) ₄] detectable. The intermediate 2 was synthesised and characterised. The formation of the undesired complex [CoH(CO)₂{P(O-2,4-t-Bu ₂C₆H₃)₃}₂] was completely suppressed due to the large cone angle of the sterically demanding phosphite.

Original language	English
Pages (from-to)	676-693
Number of pages	18
Journal	Helvetica Chimica Acta
Volume	88
Issue number	3
DOIs	https://doi.org/10.1002/hlca.200590047
Publication status	Published - 2005

ASJC Scopus subject areas

Catalysis
Biochemistry
Drug Discovery
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Synthesis, spectroscopy, and hydroformylation activity of sterically demanding, phosphite-modified cobalt catalysts",

abstract = "The dinuclear complex [Co2(CO)6{P(O-2,4-t-Bu 2C6H3)3}2] (6) has been synthesised and fully characterised. X-Ray crystal-structure analysis revealed a trans-diaxial geometry, no bridging carbonyls, and Co-Co and Co-P bond lengths of 2.706(5) and 2.134(4) {\AA}, respectively. The hydroformylation of pent-1-ene in the presence of 6 was studied at 120-180° at pressures between 20 and 80 bar Syngas. High-pressure (HP) spectroscopy (IR, NMR) was used to detect potential hydride intermediates. HP-IR Studies revealed the formation of [CoH(CO)3{P(O-2,4-t-Bu2C6H3) 3}] (2) at ca. 105°, with no significant amount of [CoH(CO) 4] detectable. The intermediate 2 was synthesised and characterised. The formation of the undesired complex [CoH(CO)2{P(O-2,4-t-Bu 2C6H3)3}2] was completely suppressed due to the large cone angle of the sterically demanding phosphite.",

author = "Reinout Meijboom and Marco Haumann and Andreas Roodt and Llewellyn Damoense",

year = "2005",

doi = "10.1002/hlca.200590047",

language = "English",

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pages = "676--693",

journal = "Helvetica Chimica Acta",

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T1 - Synthesis, spectroscopy, and hydroformylation activity of sterically demanding, phosphite-modified cobalt catalysts

AU - Meijboom, Reinout

AU - Haumann, Marco

AU - Roodt, Andreas

AU - Damoense, Llewellyn

PY - 2005

Y1 - 2005

N2 - The dinuclear complex [Co2(CO)6{P(O-2,4-t-Bu 2C6H3)3}2] (6) has been synthesised and fully characterised. X-Ray crystal-structure analysis revealed a trans-diaxial geometry, no bridging carbonyls, and Co-Co and Co-P bond lengths of 2.706(5) and 2.134(4) Å, respectively. The hydroformylation of pent-1-ene in the presence of 6 was studied at 120-180° at pressures between 20 and 80 bar Syngas. High-pressure (HP) spectroscopy (IR, NMR) was used to detect potential hydride intermediates. HP-IR Studies revealed the formation of [CoH(CO)3{P(O-2,4-t-Bu2C6H3) 3}] (2) at ca. 105°, with no significant amount of [CoH(CO) 4] detectable. The intermediate 2 was synthesised and characterised. The formation of the undesired complex [CoH(CO)2{P(O-2,4-t-Bu 2C6H3)3}2] was completely suppressed due to the large cone angle of the sterically demanding phosphite.

AB - The dinuclear complex [Co2(CO)6{P(O-2,4-t-Bu 2C6H3)3}2] (6) has been synthesised and fully characterised. X-Ray crystal-structure analysis revealed a trans-diaxial geometry, no bridging carbonyls, and Co-Co and Co-P bond lengths of 2.706(5) and 2.134(4) Å, respectively. The hydroformylation of pent-1-ene in the presence of 6 was studied at 120-180° at pressures between 20 and 80 bar Syngas. High-pressure (HP) spectroscopy (IR, NMR) was used to detect potential hydride intermediates. HP-IR Studies revealed the formation of [CoH(CO)3{P(O-2,4-t-Bu2C6H3) 3}] (2) at ca. 105°, with no significant amount of [CoH(CO) 4] detectable. The intermediate 2 was synthesised and characterised. The formation of the undesired complex [CoH(CO)2{P(O-2,4-t-Bu 2C6H3)3}2] was completely suppressed due to the large cone angle of the sterically demanding phosphite.

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DO - 10.1002/hlca.200590047

M3 - Article

AN - SCOPUS:16444376647

SN - 0018-019X

VL - 88

SP - 676

EP - 693

JO - Helvetica Chimica Acta

JF - Helvetica Chimica Acta

IS - 3

ER -

Synthesis, spectroscopy, and hydroformylation activity of sterically demanding, phosphite-modified cobalt catalysts

Abstract

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