Preparation, Crystal Structure, and Low-Temperature 1H NMR Study of (η5-C5Me5)Fe(CO)2(η1-C5H5). Reaction of (η5-C5R5)Fe(CO)2(η1-C5H5) (R = Me, H) with Bis(trifluoromethyl)ketene

Michael E. Wright; Gregory O. Nelson; Richard S. Glass

doi:10.1021/om00121a007

Preparation, Crystal Structure, and Low-Temperature ¹H NMR Study of (η⁵-C₅Me₅)Fe(CO)₂(η¹-C₅H₅). Reaction of (η⁵-C₅R₅)Fe(CO)₂(η¹-C₅H₅) (R = Me, H) with Bis(trifluoromethyl)ketene

Michael E. Wright, Gregory O. Nelson, Richard S. Glass

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

23 Scopus citations

Abstract

Sequential reaction of (η⁵-C₅Me₅)Fe(CO)₂I with silver tetrafluoroborate, cyclopentadiene, and finally triethylamine affords the new compound (η⁵-C₅Me₅)Fe(CO)₂(η¹-C₅H₅) (2) in 75% yield. Reaction of 2 with dimethyl fumarate in dichloromethane gives the [3 + 2] cycloadduct dimethyl 7-syn-[(η⁵-C₅Me₅)Fe(CO)₂]bicyclo[2.2.1]hept-5-ene-2-endo,3-exo-dicarboxylate in 90% yield. Competitive cycloaddition of the η¹-C₅H₅ moiety in (η⁵-C₅H₅)Fe(CO)₂(η¹-C₅H₅) (1) and 2 with dimethyl fumarate reveals 2 to be ca. 5 times more reactive. Reaction of 1 and 2 with bis(trifluoromethyl)ketene produces the unexpected and unique 2:1 adducts [(η⁵-C₅R₆)Fe(CO)₂](1,3-bis[(CF₃)₂CHCO]cyclopentadienyl} (4, R = H; 5, R = Me). The molecular and crystal structure for 2 is presented. Complex 2 crystallizes in the monoclinic space group P2₁/n with a = 8.591 (2) Å, b = 36.347 (13) Å, c = 10.119 (3) Å, β= 92.71 (2)°, and Z = 8. The structural parameters are refined to convergence with R₁= 0.063 and R₂= 0.084 for 2563 reflections having I > 3σ(I). A low-temperature ¹H NMR study reveals that the η¹-C₅H₅ ligand in 2 possesses increased fluxionality relative to analogue 1. The increased fluxionality of the η¹-C₅H₅ ring in 2 is attributed to a combination of electronic and steric differences of the η⁵-C₅Me₅ ligand relative to the η⁵-C₅H₅ group.

Original language	English (US)
Pages (from-to)	245-250
Number of pages	6
Journal	Organometallics
Volume	4
Issue number	2
DOIs	https://doi.org/10.1021/om00121a007
State	Published - Feb 1985
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{c8ab0ffcd30c479cb69f4650255737f4,

title = "Preparation, Crystal Structure, and Low-Temperature 1H NMR Study of (η5-C5Me5)Fe(CO)2(η1-C5H5). Reaction of (η5-C5R5)Fe(CO)2(η1-C5H5) (R = Me, H) with Bis(trifluoromethyl)ketene",

abstract = "Sequential reaction of (η5-C5Me5)Fe(CO)2I with silver tetrafluoroborate, cyclopentadiene, and finally triethylamine affords the new compound (η5-C5Me5)Fe(CO)2(η1-C5H5) (2) in 75% yield. Reaction of 2 with dimethyl fumarate in dichloromethane gives the [3 + 2] cycloadduct dimethyl 7-syn-[(η5-C5Me5)Fe(CO)2]bicyclo[2.2.1]hept-5-ene-2-endo,3-exo-dicarboxylate in 90% yield. Competitive cycloaddition of the η1-C5H5 moiety in (η5-C5H5)Fe(CO)2(η1-C5H5) (1) and 2 with dimethyl fumarate reveals 2 to be ca. 5 times more reactive. Reaction of 1 and 2 with bis(trifluoromethyl)ketene produces the unexpected and unique 2:1 adducts [(η5-C5R6)Fe(CO)2](1,3-bis[(CF3)2CHCO]cyclopentadienyl} (4, R = H; 5, R = Me). The molecular and crystal structure for 2 is presented. Complex 2 crystallizes in the monoclinic space group P21/n with a = 8.591 (2) {\AA}, b = 36.347 (13) {\AA}, c = 10.119 (3) {\AA}, β= 92.71 (2)°, and Z = 8. The structural parameters are refined to convergence with R1= 0.063 and R2= 0.084 for 2563 reflections having I > 3σ(I). A low-temperature 1H NMR study reveals that the η1-C5H5 ligand in 2 possesses increased fluxionality relative to analogue 1. The increased fluxionality of the η1-C5H5 ring in 2 is attributed to a combination of electronic and steric differences of the η5-C5Me5 ligand relative to the η5-C5H5 group.",

author = "Wright, {Michael E.} and Nelson, {Gregory O.} and Glass, {Richard S.}",

year = "1985",

month = feb,

doi = "10.1021/om00121a007",

language = "English (US)",

volume = "4",

pages = "245--250",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Preparation, Crystal Structure, and Low-Temperature 1H NMR Study of (η5-C5Me5)Fe(CO)2(η1-C5H5). Reaction of (η5-C5R5)Fe(CO)2(η1-C5H5) (R = Me, H) with Bis(trifluoromethyl)ketene

AU - Wright, Michael E.

AU - Nelson, Gregory O.

AU - Glass, Richard S.

PY - 1985/2

Y1 - 1985/2

N2 - Sequential reaction of (η5-C5Me5)Fe(CO)2I with silver tetrafluoroborate, cyclopentadiene, and finally triethylamine affords the new compound (η5-C5Me5)Fe(CO)2(η1-C5H5) (2) in 75% yield. Reaction of 2 with dimethyl fumarate in dichloromethane gives the [3 + 2] cycloadduct dimethyl 7-syn-[(η5-C5Me5)Fe(CO)2]bicyclo[2.2.1]hept-5-ene-2-endo,3-exo-dicarboxylate in 90% yield. Competitive cycloaddition of the η1-C5H5 moiety in (η5-C5H5)Fe(CO)2(η1-C5H5) (1) and 2 with dimethyl fumarate reveals 2 to be ca. 5 times more reactive. Reaction of 1 and 2 with bis(trifluoromethyl)ketene produces the unexpected and unique 2:1 adducts [(η5-C5R6)Fe(CO)2](1,3-bis[(CF3)2CHCO]cyclopentadienyl} (4, R = H; 5, R = Me). The molecular and crystal structure for 2 is presented. Complex 2 crystallizes in the monoclinic space group P21/n with a = 8.591 (2) Å, b = 36.347 (13) Å, c = 10.119 (3) Å, β= 92.71 (2)°, and Z = 8. The structural parameters are refined to convergence with R1= 0.063 and R2= 0.084 for 2563 reflections having I > 3σ(I). A low-temperature 1H NMR study reveals that the η1-C5H5 ligand in 2 possesses increased fluxionality relative to analogue 1. The increased fluxionality of the η1-C5H5 ring in 2 is attributed to a combination of electronic and steric differences of the η5-C5Me5 ligand relative to the η5-C5H5 group.

AB - Sequential reaction of (η5-C5Me5)Fe(CO)2I with silver tetrafluoroborate, cyclopentadiene, and finally triethylamine affords the new compound (η5-C5Me5)Fe(CO)2(η1-C5H5) (2) in 75% yield. Reaction of 2 with dimethyl fumarate in dichloromethane gives the [3 + 2] cycloadduct dimethyl 7-syn-[(η5-C5Me5)Fe(CO)2]bicyclo[2.2.1]hept-5-ene-2-endo,3-exo-dicarboxylate in 90% yield. Competitive cycloaddition of the η1-C5H5 moiety in (η5-C5H5)Fe(CO)2(η1-C5H5) (1) and 2 with dimethyl fumarate reveals 2 to be ca. 5 times more reactive. Reaction of 1 and 2 with bis(trifluoromethyl)ketene produces the unexpected and unique 2:1 adducts [(η5-C5R6)Fe(CO)2](1,3-bis[(CF3)2CHCO]cyclopentadienyl} (4, R = H; 5, R = Me). The molecular and crystal structure for 2 is presented. Complex 2 crystallizes in the monoclinic space group P21/n with a = 8.591 (2) Å, b = 36.347 (13) Å, c = 10.119 (3) Å, β= 92.71 (2)°, and Z = 8. The structural parameters are refined to convergence with R1= 0.063 and R2= 0.084 for 2563 reflections having I > 3σ(I). A low-temperature 1H NMR study reveals that the η1-C5H5 ligand in 2 possesses increased fluxionality relative to analogue 1. The increased fluxionality of the η1-C5H5 ring in 2 is attributed to a combination of electronic and steric differences of the η5-C5Me5 ligand relative to the η5-C5H5 group.

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Preparation, Crystal Structure, and Low-Temperature ¹H NMR Study of (η⁵-C₅Me₅)Fe(CO)₂(η¹-C₅H₅). Reaction of (η⁵-C₅R₅)Fe(CO)₂(η¹-C₅H₅) (R = Me, H) with Bis(trifluoromethyl)ketene

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