Reactions of Organocopper Reagents with the Cationic Bridging Acylium Complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+

Charles P. Casey; Mark Crocker; Paul C. Vosejpka; Arnold L. Rheingold

doi:10.1021/om00104a002

Reactions of Organocopper Reagents with the Cationic Bridging Acylium Complex [C₅H₅(CO)Fe]₂(μ-CO)(μ-CHCO)⁺

Charles P. Casey
, Mark Crocker
, Paul C. Vosejpka
, Arnold L. Rheingold

Chemistry

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

15 Scopus citations

Abstract

The bridging acylium complex [C₅H₅(CO)Fe]₂(μ-CO)(μ-CHCO)⁺PF₆^- (2) reacted with organocuprates Li(RCuCN) at the acylium carbon to give the acyl-substituted μ-alkylidene complexes [C₅H₅(CO)Fe]₂(μ-CO)(μ-CHCOR) (6, R = CH₃; 7, R = (CH₂)₃CH₃; 8, R = C₆H₅). The acyl groups of complexes 6–8 display low carbonyl stretching frequencies indicative of strong electron donation from the Fe₂(μ-C) core onto the acyl substituents. The molecular structure of 8, determined by X-ray crystallography, supports these observations. Crystals of 8 are triclinic, space group PI, with a = 7.008 (2) Å, b = 12.392 (3) Å, c = 12.441 (3) Å, α = 118.37 (2)°, β = 91.09 (2)°, γ = 103.42 (2)°, and Z = 2. 6 reacted with CF₃S0₃CH₃ to give the O-methylated complex [C₅H₅(CO)Fe]₂(μ-CO)[μ-CHC(CH₃)OCH₃]⁺CF₃SO₃^- (12) resulting from methylation of the acetyl group of 6 at oxygen. Reaction of 2 with Li₂[(CH₃)₂CuCN] afforded the μ-alkenylidene complex [C₅H₅(CO)Fe]₂(μ-CO)[μ-C=(CH₃)₂] (13) via double nucleophilic addition. 13 reacted with Me₃O⁺BF₄^- to give the μ-alkylidyne complex [C₅H₅(CO)Fe]2(μ-CO)[μ-CC(CH₃)₃]⁺BF4^- (14).

Original language	English
Pages (from-to)	278-282
Number of pages	5
Journal	Organometallics
Volume	8
Issue number	2
DOIs	https://doi.org/10.1021/om00104a002
State	Published - Feb 1989

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{3918439ba63646cf893c9d2dafbb7f0f,

title = "Reactions of Organocopper Reagents with the Cationic Bridging Acylium Complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+",

abstract = "The bridging acylium complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+PF6- (2) reacted with organocuprates Li(RCuCN) at the acylium carbon to give the acyl-substituted μ-alkylidene complexes [C5H5(CO)Fe]2(μ-CO)(μ-CHCOR) (6, R = CH3; 7, R = (CH2)3CH3; 8, R = C6H5). The acyl groups of complexes 6–8 display low carbonyl stretching frequencies indicative of strong electron donation from the Fe2(μ-C) core onto the acyl substituents. The molecular structure of 8, determined by X-ray crystallography, supports these observations. Crystals of 8 are triclinic, space group PI, with a = 7.008 (2) {\AA}, b = 12.392 (3) {\AA}, c = 12.441 (3) {\AA}, α = 118.37 (2)°, β = 91.09 (2)°, γ = 103.42 (2)°, and Z = 2. 6 reacted with CF3S03CH3 to give the O-methylated complex [C5H5(CO)Fe]2(μ-CO)[μ-CHC(CH3)OCH3]+CF3SO3- (12) resulting from methylation of the acetyl group of 6 at oxygen. Reaction of 2 with Li2[(CH3)2CuCN] afforded the μ-alkenylidene complex [C5H5(CO)Fe]2(μ-CO)[μ-C=(CH3)2] (13) via double nucleophilic addition. 13 reacted with Me3O+BF4- to give the μ-alkylidyne complex [C5H5(CO)Fe]2(μ-CO)[μ-CC(CH3)3]+BF4- (14).",

author = "Casey, \{Charles P.\} and Mark Crocker and Vosejpka, \{Paul C.\} and Rheingold, \{Arnold L.\}",

year = "1989",

month = feb,

doi = "10.1021/om00104a002",

language = "English",

volume = "8",

pages = "278--282",

number = "2",

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TY - JOUR

T1 - Reactions of Organocopper Reagents with the Cationic Bridging Acylium Complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+

AU - Casey, Charles P.

AU - Crocker, Mark

AU - Vosejpka, Paul C.

AU - Rheingold, Arnold L.

PY - 1989/2

Y1 - 1989/2

N2 - The bridging acylium complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+PF6- (2) reacted with organocuprates Li(RCuCN) at the acylium carbon to give the acyl-substituted μ-alkylidene complexes [C5H5(CO)Fe]2(μ-CO)(μ-CHCOR) (6, R = CH3; 7, R = (CH2)3CH3; 8, R = C6H5). The acyl groups of complexes 6–8 display low carbonyl stretching frequencies indicative of strong electron donation from the Fe2(μ-C) core onto the acyl substituents. The molecular structure of 8, determined by X-ray crystallography, supports these observations. Crystals of 8 are triclinic, space group PI, with a = 7.008 (2) Å, b = 12.392 (3) Å, c = 12.441 (3) Å, α = 118.37 (2)°, β = 91.09 (2)°, γ = 103.42 (2)°, and Z = 2. 6 reacted with CF3S03CH3 to give the O-methylated complex [C5H5(CO)Fe]2(μ-CO)[μ-CHC(CH3)OCH3]+CF3SO3- (12) resulting from methylation of the acetyl group of 6 at oxygen. Reaction of 2 with Li2[(CH3)2CuCN] afforded the μ-alkenylidene complex [C5H5(CO)Fe]2(μ-CO)[μ-C=(CH3)2] (13) via double nucleophilic addition. 13 reacted with Me3O+BF4- to give the μ-alkylidyne complex [C5H5(CO)Fe]2(μ-CO)[μ-CC(CH3)3]+BF4- (14).

AB - The bridging acylium complex [C5H5(CO)Fe]2(μ-CO)(μ-CHCO)+PF6- (2) reacted with organocuprates Li(RCuCN) at the acylium carbon to give the acyl-substituted μ-alkylidene complexes [C5H5(CO)Fe]2(μ-CO)(μ-CHCOR) (6, R = CH3; 7, R = (CH2)3CH3; 8, R = C6H5). The acyl groups of complexes 6–8 display low carbonyl stretching frequencies indicative of strong electron donation from the Fe2(μ-C) core onto the acyl substituents. The molecular structure of 8, determined by X-ray crystallography, supports these observations. Crystals of 8 are triclinic, space group PI, with a = 7.008 (2) Å, b = 12.392 (3) Å, c = 12.441 (3) Å, α = 118.37 (2)°, β = 91.09 (2)°, γ = 103.42 (2)°, and Z = 2. 6 reacted with CF3S03CH3 to give the O-methylated complex [C5H5(CO)Fe]2(μ-CO)[μ-CHC(CH3)OCH3]+CF3SO3- (12) resulting from methylation of the acetyl group of 6 at oxygen. Reaction of 2 with Li2[(CH3)2CuCN] afforded the μ-alkenylidene complex [C5H5(CO)Fe]2(μ-CO)[μ-C=(CH3)2] (13) via double nucleophilic addition. 13 reacted with Me3O+BF4- to give the μ-alkylidyne complex [C5H5(CO)Fe]2(μ-CO)[μ-CC(CH3)3]+BF4- (14).

UR - https://www.scopus.com/pages/publications/2642662872

UR - https://www.scopus.com/pages/publications/2642662872#tab=citedBy

U2 - 10.1021/om00104a002

DO - 10.1021/om00104a002

M3 - Article

AN - SCOPUS:2642662872

SN - 0276-7333

VL - 8

SP - 278

EP - 282

JO - Organometallics

JF - Organometallics

IS - 2

ER -

Reactions of Organocopper Reagents with the Cationic Bridging Acylium Complex [C₅H₅(CO)Fe]₂(μ-CO)(μ-CHCO)⁺

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