New iron complexes from nucleophile addition/carbonylation of η4-(1,3-diene)tricarbonyliron(0) complexes

M. F. Semmelhack; James W. Herndon

doi:10.1016/0022-328X(84)80077-7

New iron complexes from nucleophile addition/carbonylation of η⁴-(1,3-diene)tricarbonyliron(0) complexes

M. F. Semmelhack, James W. Herndon

Chemistry

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

23 Scopus citations

Abstract

A series of novel organoiron complexes has been isolated and studied by ¹H NMR, ¹³C NMR, and IR spectroscopy. Addition of LiC(CH₃)₂CN to (1,3-cyclohexadiene)tricarbonyliron produces an intermediate which is only stable at low temperature and which is assigned the homoallyl-Fe(CO)₃ anion structure. The intermediate rearranges on warming into a stable complex, for which full spectral data support the structure as an allyl-Fe(CO)₃ anionic species. Interception of the first formed intermediate with CO gives an acylferrate complex with an olefin unit still bound to iron, and methylation then occurs at oxygen to produce an unusual internally-bound (alkene)(methoxyalkylidene)tricarbonyliron species.

Original language	English (US)
Pages (from-to)	c15-c18
Journal	Journal of Organometallic Chemistry
Volume	265
Issue number	2
DOIs	https://doi.org/10.1016/0022-328X(84)80077-7
State	Published - Apr 10 1984

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/0022-328X(84)80077-7

Cite this

@article{78d3b254aefc4cc8a2bcb90b07934a9f,

title = "New iron complexes from nucleophile addition/carbonylation of η4-(1,3-diene)tricarbonyliron(0) complexes",

abstract = "A series of novel organoiron complexes has been isolated and studied by 1H NMR, 13C NMR, and IR spectroscopy. Addition of LiC(CH3)2CN to (1,3-cyclohexadiene)tricarbonyliron produces an intermediate which is only stable at low temperature and which is assigned the homoallyl-Fe(CO)3 anion structure. The intermediate rearranges on warming into a stable complex, for which full spectral data support the structure as an allyl-Fe(CO)3 anionic species. Interception of the first formed intermediate with CO gives an acylferrate complex with an olefin unit still bound to iron, and methylation then occurs at oxygen to produce an unusual internally-bound (alkene)(methoxyalkylidene)tricarbonyliron species.",

author = "Semmelhack, {M. F.} and Herndon, {James W.}",

note = "Funding Information: Acknowledgements, We are pleased to acknowledge financial support of this work in the form of a researchg rant to MFS (National Science Foundation; CHE 8204339) and fellowships to JWH (NIH Graduate Trainee: 1981-1982; Exxon Fellow, 1982-1983). We also thank Ms. Mary Baum for assistancei n obtaining the NMR data.",

year = "1984",

month = apr,

day = "10",

doi = "10.1016/0022-328X(84)80077-7",

language = "English (US)",

volume = "265",

pages = "c15--c18",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "2",

}

TY - JOUR

T1 - New iron complexes from nucleophile addition/carbonylation of η4-(1,3-diene)tricarbonyliron(0) complexes

AU - Semmelhack, M. F.

AU - Herndon, James W.

N1 - Funding Information: Acknowledgements, We are pleased to acknowledge financial support of this work in the form of a researchg rant to MFS (National Science Foundation; CHE 8204339) and fellowships to JWH (NIH Graduate Trainee: 1981-1982; Exxon Fellow, 1982-1983). We also thank Ms. Mary Baum for assistancei n obtaining the NMR data.

PY - 1984/4/10

Y1 - 1984/4/10

N2 - A series of novel organoiron complexes has been isolated and studied by 1H NMR, 13C NMR, and IR spectroscopy. Addition of LiC(CH3)2CN to (1,3-cyclohexadiene)tricarbonyliron produces an intermediate which is only stable at low temperature and which is assigned the homoallyl-Fe(CO)3 anion structure. The intermediate rearranges on warming into a stable complex, for which full spectral data support the structure as an allyl-Fe(CO)3 anionic species. Interception of the first formed intermediate with CO gives an acylferrate complex with an olefin unit still bound to iron, and methylation then occurs at oxygen to produce an unusual internally-bound (alkene)(methoxyalkylidene)tricarbonyliron species.

AB - A series of novel organoiron complexes has been isolated and studied by 1H NMR, 13C NMR, and IR spectroscopy. Addition of LiC(CH3)2CN to (1,3-cyclohexadiene)tricarbonyliron produces an intermediate which is only stable at low temperature and which is assigned the homoallyl-Fe(CO)3 anion structure. The intermediate rearranges on warming into a stable complex, for which full spectral data support the structure as an allyl-Fe(CO)3 anionic species. Interception of the first formed intermediate with CO gives an acylferrate complex with an olefin unit still bound to iron, and methylation then occurs at oxygen to produce an unusual internally-bound (alkene)(methoxyalkylidene)tricarbonyliron species.

UR - http://www.scopus.com/inward/record.url?scp=4243718764&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=4243718764&partnerID=8YFLogxK

U2 - 10.1016/0022-328X(84)80077-7

DO - 10.1016/0022-328X(84)80077-7

M3 - Article

AN - SCOPUS:4243718764

SN - 0022-328X

VL - 265

SP - c15-c18

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2

ER -

New iron complexes from nucleophile addition/carbonylation of η⁴-(1,3-diene)tricarbonyliron(0) complexes

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this