Structure and Reactivity of (η5-C5H5)Mn(CO)2in Room-Temperature Solution: Evidence for Formation of a Dinuclear Intermediate Detected by Flash Photolysis and Time-Resolved Infrared Spectroscopy

Bernadette S. Creaven; Andrew J. Dixon; John M. Kelly; Conor Long; Martyn Poliakoff

doi:10.1021/om00155a026

Structure and Reactivity of (η⁵-C₅H₅)Mn(CO)₂in Room-Temperature Solution: Evidence for Formation of a Dinuclear Intermediate Detected by Flash Photolysis and Time-Resolved Infrared Spectroscopy

Bernadette S. Creaven, Andrew J. Dixon, John M. Kelly, Conor Long, Martyn Poliakoff

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

Abstract

UV laser flash photolysis (308 nm, 15 ns) with UV/vis monitoring and with time-resolved IR spectroscopy has been used to characterize two transient species formed by the photolysis of CpMn(CO)₃(Cp = η⁵-C₅H₅) in alkane solution. The first species has been identified as CpMn(GO)₂S where S = cyclohexane or n-heptane, from both its kinetic behavior and its IR spectrum. CpMn(CO)₂S reacts with CO, N₂, and PPh₃with bimolecular rate constants similar to those previously published for the corresponding reactions of the group 6 metal pentacarbonyls. The second transient species Cp₂Mn₂(CO)₅is formed by the reacton of CpMn(CO)₂S with unphotolyzed CpMn(CO)₃.¹³CO enrichment and IR spectroscopy are used to establish that Cp₂Mn₂(CO)₅has a single bridging CO group. The formation of Cp₂Mn₂(CO)₅can be suppressed by reagents, e.g. PPh₃, added to the solution.

Original language	English
Pages (from-to)	2600-2605
Number of pages	6
Journal	Organometallics
Volume	6
Issue number	12
DOIs	https://doi.org/10.1021/om00155a026
Publication status	Published - 1 Dec 1987
Externally published	Yes

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@article{e0710fdca7fb4666a8ef359c21805d86,

title = "Structure and Reactivity of (η5-C5H5)Mn(CO)2in Room-Temperature Solution: Evidence for Formation of a Dinuclear Intermediate Detected by Flash Photolysis and Time-Resolved Infrared Spectroscopy",

abstract = "UV laser flash photolysis (308 nm, 15 ns) with UV/vis monitoring and with time-resolved IR spectroscopy has been used to characterize two transient species formed by the photolysis of CpMn(CO)3(Cp = η5-C5H5) in alkane solution. The first species has been identified as CpMn(GO)2S where S = cyclohexane or n-heptane, from both its kinetic behavior and its IR spectrum. CpMn(CO)2S reacts with CO, N2, and PPh3with bimolecular rate constants similar to those previously published for the corresponding reactions of the group 6 metal pentacarbonyls. The second transient species Cp2Mn2(CO)5is formed by the reacton of CpMn(CO)2S with unphotolyzed CpMn(CO)3.13CO enrichment and IR spectroscopy are used to establish that Cp2Mn2(CO)5has a single bridging CO group. The formation of Cp2Mn2(CO)5can be suppressed by reagents, e.g. PPh3, added to the solution.",

author = "Creaven, {Bernadette S.} and Dixon, {Andrew J.} and Kelly, {John M.} and Conor Long and Martyn Poliakoff",

year = "1987",

month = dec,

day = "1",

doi = "10.1021/om00155a026",

language = "English",

volume = "6",

pages = "2600--2605",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

Structure and Reactivity of (η⁵-C₅H₅)Mn(CO)₂in Room-Temperature Solution: Evidence for Formation of a Dinuclear Intermediate Detected by Flash Photolysis and Time-Resolved Infrared Spectroscopy. / Creaven, Bernadette S.; Dixon, Andrew J.; Kelly, John M. et al.
In: Organometallics, Vol. 6, No. 12, 01.12.1987, p. 2600-2605.

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

TY - JOUR

T1 - Structure and Reactivity of (η5-C5H5)Mn(CO)2in Room-Temperature Solution

T2 - Evidence for Formation of a Dinuclear Intermediate Detected by Flash Photolysis and Time-Resolved Infrared Spectroscopy

AU - Creaven, Bernadette S.

AU - Dixon, Andrew J.

AU - Kelly, John M.

AU - Long, Conor

AU - Poliakoff, Martyn

PY - 1987/12/1

Y1 - 1987/12/1

N2 - UV laser flash photolysis (308 nm, 15 ns) with UV/vis monitoring and with time-resolved IR spectroscopy has been used to characterize two transient species formed by the photolysis of CpMn(CO)3(Cp = η5-C5H5) in alkane solution. The first species has been identified as CpMn(GO)2S where S = cyclohexane or n-heptane, from both its kinetic behavior and its IR spectrum. CpMn(CO)2S reacts with CO, N2, and PPh3with bimolecular rate constants similar to those previously published for the corresponding reactions of the group 6 metal pentacarbonyls. The second transient species Cp2Mn2(CO)5is formed by the reacton of CpMn(CO)2S with unphotolyzed CpMn(CO)3.13CO enrichment and IR spectroscopy are used to establish that Cp2Mn2(CO)5has a single bridging CO group. The formation of Cp2Mn2(CO)5can be suppressed by reagents, e.g. PPh3, added to the solution.

AB - UV laser flash photolysis (308 nm, 15 ns) with UV/vis monitoring and with time-resolved IR spectroscopy has been used to characterize two transient species formed by the photolysis of CpMn(CO)3(Cp = η5-C5H5) in alkane solution. The first species has been identified as CpMn(GO)2S where S = cyclohexane or n-heptane, from both its kinetic behavior and its IR spectrum. CpMn(CO)2S reacts with CO, N2, and PPh3with bimolecular rate constants similar to those previously published for the corresponding reactions of the group 6 metal pentacarbonyls. The second transient species Cp2Mn2(CO)5is formed by the reacton of CpMn(CO)2S with unphotolyzed CpMn(CO)3.13CO enrichment and IR spectroscopy are used to establish that Cp2Mn2(CO)5has a single bridging CO group. The formation of Cp2Mn2(CO)5can be suppressed by reagents, e.g. PPh3, added to the solution.

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DO - 10.1021/om00155a026

M3 - Article

AN - SCOPUS:0000578682

SN - 0276-7333

VL - 6

SP - 2600

EP - 2605

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Structure and Reactivity of (η5-C5H5)Mn(CO)2in Room-Temperature Solution: Evidence for Formation of a Dinuclear Intermediate Detected by Flash Photolysis and Time-Resolved Infrared Spectroscopy

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Structure and Reactivity of (η⁵-C₅H₅)Mn(CO)₂in Room-Temperature Solution: Evidence for Formation of a Dinuclear Intermediate Detected by Flash Photolysis and Time-Resolved Infrared Spectroscopy