Kinetics of nucleophilic addition of tertiary phosphines to dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation

David M. Birney; Annette M. Crane; D. A. Sweigart

doi:10.1016/S0022-328X(00)91920-X

Kinetics of nucleophilic addition of tertiary phosphines to dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation

David M. Birney, Annette M. Crane, D. A. Sweigart

Chemistry and Biochemistry

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Abstract

Tertiary phosphines rapidly add to the ring in dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation to form phosphonium adducts. Kinetic studies of this reaction support a mechanism consisting of direct bimolecular attack on the ring. Reactivity towards nucleophilic attack by phosphines follows the order: [(C₇H₈)Mn(CO)₃]⁺ > [(C₄H₄)Fe(CO)₂NO]⁺ > [(C₆H₇)Fe(CO)₃]⁺ > [(C₆H₆OMe)Fe(CO)₃]⁺ ≳ [(C₇H₇)M(CO)₃]⁺ (M = Cr, Mo, W) > [(C₆H₆)Mn(CO)₃]⁺. Coordinated cycloheptatriene is about 10⁴ times more electrophilic towards phosphine nucleophiles than is coordinated benzene.

Original language	English
Pages (from-to)	187-192
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	152
Issue number	2
DOIs	https://doi.org/10.1016/S0022-328X(00)91920-X
State	Published - May 30 1978

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@article{f4beae88a502493daebb15aa9da74816,

title = "Kinetics of nucleophilic addition of tertiary phosphines to dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation",

abstract = "Tertiary phosphines rapidly add to the ring in dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation to form phosphonium adducts. Kinetic studies of this reaction support a mechanism consisting of direct bimolecular attack on the ring. Reactivity towards nucleophilic attack by phosphines follows the order: [(C7H8)Mn(CO)3]+ > [(C4H4)Fe(CO)2NO]+ > [(C6H7)Fe(CO)3]+ > [(C6H6OMe)Fe(CO)3]+ ≳ [(C7H7)M(CO)3]+ (M = Cr, Mo, W) > [(C6H6)Mn(CO)3]+. Coordinated cycloheptatriene is about 104 times more electrophilic towards phosphine nucleophiles than is coordinated benzene.",

author = "Birney, {David M.} and Crane, {Annette M.} and Sweigart, {D. A.}",

note = "Funding Information: Acknowledgement is made to the donors of the Petroleum Research Fund, administrered by the American Chemical Society, for support of this research.",

year = "1978",

month = may,

day = "30",

doi = "10.1016/S0022-328X(00)91920-X",

language = "English",

volume = "152",

pages = "187--192",

journal = "Journal of Organometallic Chemistry",

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T1 - Kinetics of nucleophilic addition of tertiary phosphines to dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation

AU - Birney, David M.

AU - Crane, Annette M.

AU - Sweigart, D. A.

N1 - Funding Information: Acknowledgement is made to the donors of the Petroleum Research Fund, administrered by the American Chemical Society, for support of this research.

PY - 1978/5/30

Y1 - 1978/5/30

N2 - Tertiary phosphines rapidly add to the ring in dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation to form phosphonium adducts. Kinetic studies of this reaction support a mechanism consisting of direct bimolecular attack on the ring. Reactivity towards nucleophilic attack by phosphines follows the order: [(C7H8)Mn(CO)3]+ > [(C4H4)Fe(CO)2NO]+ > [(C6H7)Fe(CO)3]+ > [(C6H6OMe)Fe(CO)3]+ ≳ [(C7H7)M(CO)3]+ (M = Cr, Mo, W) > [(C6H6)Mn(CO)3]+. Coordinated cycloheptatriene is about 104 times more electrophilic towards phosphine nucleophiles than is coordinated benzene.

AB - Tertiary phosphines rapidly add to the ring in dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation to form phosphonium adducts. Kinetic studies of this reaction support a mechanism consisting of direct bimolecular attack on the ring. Reactivity towards nucleophilic attack by phosphines follows the order: [(C7H8)Mn(CO)3]+ > [(C4H4)Fe(CO)2NO]+ > [(C6H7)Fe(CO)3]+ > [(C6H6OMe)Fe(CO)3]+ ≳ [(C7H7)M(CO)3]+ (M = Cr, Mo, W) > [(C6H6)Mn(CO)3]+. Coordinated cycloheptatriene is about 104 times more electrophilic towards phosphine nucleophiles than is coordinated benzene.

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U2 - 10.1016/S0022-328X(00)91920-X

DO - 10.1016/S0022-328X(00)91920-X

M3 - Article

AN - SCOPUS:49349126090

SN - 0022-328X

VL - 152

SP - 187

EP - 192

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2

ER -

Kinetics of nucleophilic addition of tertiary phosphines to dicarbonylnitrosyl(cyclobutadiene)iron cation and tricarbonyl(cycloheptatriene)manganese cation

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