Synthesis and reactivity of cyclic and acyclic (1-(acyloxy)pentadienyl)Fe(CO)2LX and (1-alkoxypentadienyl)Fe(CO)2LX salts (L = CO, PPh3)

James A.S. Howell; Andrew G. Bell; Paula J. O'Leary; G. Richard Stephenson; Michelle Hastings; Philip W. Howard; David A. Owen; Andrew J. Whitehead; Patrick McArdle; Desmond Cunningham

doi:10.1021/om960336a

Synthesis and reactivity of cyclic and acyclic (1-(acyloxy)pentadienyl)Fe(CO)₂LX and (1-alkoxypentadienyl)Fe(CO)₂LX salts (L = CO, PPh₃)

James A.S. Howell, Andrew G. Bell, Paula J. O'Leary, G. Richard Stephenson, Michelle Hastings, Philip W. Howard, David A. Owen, Andrew J. Whitehead, Patrick McArdle, Desmond Cunningham

Research output: Contribution to a Journal (Peer & Non Peer) › Article › peer-review

16 Citations (Scopus)

Abstract

A variety of cyclic and acyclic [(pentadienyl)Fe(CO)₂L]X complexes (L = CO, PPh3) containing terminal acyloxy or alkoxy substituents have been prepared. In situ NMR studies indicate that for the acyclic series where L = CO, stability is limited by solvolysis reactions. The position of nucleophilic attack (ipso for alkoxy, internal for acyloxy) in the acyclic series indicates an electron-donating and electron-withdrawing nature for alkoxy and acyloxy substituents, respectively. In the cyclic series, the different regiodirecting powers of alkoxy and acyloxy groups provide access to regioisomeric substituted cyclohexadienyl salts. Crystal structures of the ψ-exo and ψ-endo stereoisomers of [5-(benzoyloxy)-2,4-hexadien-1-ol]Fe-(CO)₂PPh₃ (34 and 35) and of [(1,3,4,5-η)-1-(benzoyloxy)-2-methyl-3-pentene-1,5-diyl]Fe-(CO) ₂PPh₃ (57) have been determined.

Original language	English
Pages (from-to)	4247-4257
Number of pages	11
Journal	Organometallics
Volume	15
Issue number	20
DOIs	https://doi.org/10.1021/om960336a
Publication status	Published - 1 Oct 1996
Externally published	Yes

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Howell, J. A. S., Bell, A. G., O'Leary, P. J., Stephenson, G. R., Hastings, M., Howard, P. W., Owen, D. A., Whitehead, A. J., McArdle, P., & Cunningham, D. (1996). Synthesis and reactivity of cyclic and acyclic (1-(acyloxy)pentadienyl)Fe(CO)₂LX and (1-alkoxypentadienyl)Fe(CO)₂LX salts (L = CO, PPh₃). Organometallics, 15(20), 4247-4257. https://doi.org/10.1021/om960336a

@article{51f3f25c3006432094baf2930e57d657,

title = "Synthesis and reactivity of cyclic and acyclic (1-(acyloxy)pentadienyl)Fe(CO)2LX and (1-alkoxypentadienyl)Fe(CO)2LX salts (L = CO, PPh3)",

abstract = "A variety of cyclic and acyclic [(pentadienyl)Fe(CO)2L]X complexes (L = CO, PPh3) containing terminal acyloxy or alkoxy substituents have been prepared. In situ NMR studies indicate that for the acyclic series where L = CO, stability is limited by solvolysis reactions. The position of nucleophilic attack (ipso for alkoxy, internal for acyloxy) in the acyclic series indicates an electron-donating and electron-withdrawing nature for alkoxy and acyloxy substituents, respectively. In the cyclic series, the different regiodirecting powers of alkoxy and acyloxy groups provide access to regioisomeric substituted cyclohexadienyl salts. Crystal structures of the ψ-exo and ψ-endo stereoisomers of [5-(benzoyloxy)-2,4-hexadien-1-ol]Fe-(CO)2PPh3 (34 and 35) and of [(1,3,4,5-η)-1-(benzoyloxy)-2-methyl-3-pentene-1,5-diyl]Fe-(CO) 2PPh3 (57) have been determined.",

author = "Howell, \{James A.S.\} and Bell, \{Andrew G.\} and O'Leary, \{Paula J.\} and Stephenson, \{G. Richard\} and Michelle Hastings and Howard, \{Philip W.\} and Owen, \{David A.\} and Whitehead, \{Andrew J.\} and Patrick McArdle and Desmond Cunningham",

year = "1996",

month = oct,

day = "1",

doi = "10.1021/om960336a",

language = "English",

volume = "15",

pages = "4247--4257",

journal = "Organometallics",

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TY - JOUR

T1 - Synthesis and reactivity of cyclic and acyclic (1-(acyloxy)pentadienyl)Fe(CO)2LX and (1-alkoxypentadienyl)Fe(CO)2LX salts (L = CO, PPh3)

AU - Howell, James A.S.

AU - Bell, Andrew G.

AU - O'Leary, Paula J.

AU - Stephenson, G. Richard

AU - Hastings, Michelle

AU - Howard, Philip W.

AU - Owen, David A.

AU - Whitehead, Andrew J.

AU - McArdle, Patrick

AU - Cunningham, Desmond

PY - 1996/10/1

Y1 - 1996/10/1

N2 - A variety of cyclic and acyclic [(pentadienyl)Fe(CO)2L]X complexes (L = CO, PPh3) containing terminal acyloxy or alkoxy substituents have been prepared. In situ NMR studies indicate that for the acyclic series where L = CO, stability is limited by solvolysis reactions. The position of nucleophilic attack (ipso for alkoxy, internal for acyloxy) in the acyclic series indicates an electron-donating and electron-withdrawing nature for alkoxy and acyloxy substituents, respectively. In the cyclic series, the different regiodirecting powers of alkoxy and acyloxy groups provide access to regioisomeric substituted cyclohexadienyl salts. Crystal structures of the ψ-exo and ψ-endo stereoisomers of [5-(benzoyloxy)-2,4-hexadien-1-ol]Fe-(CO)2PPh3 (34 and 35) and of [(1,3,4,5-η)-1-(benzoyloxy)-2-methyl-3-pentene-1,5-diyl]Fe-(CO) 2PPh3 (57) have been determined.

AB - A variety of cyclic and acyclic [(pentadienyl)Fe(CO)2L]X complexes (L = CO, PPh3) containing terminal acyloxy or alkoxy substituents have been prepared. In situ NMR studies indicate that for the acyclic series where L = CO, stability is limited by solvolysis reactions. The position of nucleophilic attack (ipso for alkoxy, internal for acyloxy) in the acyclic series indicates an electron-donating and electron-withdrawing nature for alkoxy and acyloxy substituents, respectively. In the cyclic series, the different regiodirecting powers of alkoxy and acyloxy groups provide access to regioisomeric substituted cyclohexadienyl salts. Crystal structures of the ψ-exo and ψ-endo stereoisomers of [5-(benzoyloxy)-2,4-hexadien-1-ol]Fe-(CO)2PPh3 (34 and 35) and of [(1,3,4,5-η)-1-(benzoyloxy)-2-methyl-3-pentene-1,5-diyl]Fe-(CO) 2PPh3 (57) have been determined.

UR - https://www.scopus.com/pages/publications/0000361282

U2 - 10.1021/om960336a

DO - 10.1021/om960336a

M3 - Article

SN - 0276-7333

VL - 15

SP - 4247

EP - 4257

JO - Organometallics

JF - Organometallics

IS - 20

ER -

Synthesis and reactivity of cyclic and acyclic (1-(acyloxy)pentadienyl)Fe(CO)₂LX and (1-alkoxypentadienyl)Fe(CO)₂LX salts (L = CO, PPh₃)

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