Photoinduced Se-C insertion following photolysis of (η5- C4H4Se)Cr(CO)3. A picosecond and nanosecond time-resolved infrared, matrix isolation, and DFT investigation

Peter Brennan; Michael W. George; Omar S. Jina; Conor Long; Jennifer McKenna; Mary T. Pryce; Xue Zhong Sun; Khuong Q. Vuong

doi:10.1021/om7011979

Photoinduced Se-C insertion following photolysis of (η⁵- C₄H₄Se)Cr(CO)₃. A picosecond and nanosecond time-resolved infrared, matrix isolation, and DFT investigation

Peter Brennan, Michael W. George, Omar S. Jina, Conor Long, Jennifer McKenna, Mary T. Pryce, Xue Zhong Sun, Khuong Q. Vuong

Research output: Journal Publication › Article › peer-review

21 Citations (Scopus)

Abstract

The photochemistry of (η⁵;-C₄H ₄Se)Cr(CO)₃ was investigated by matrix isolation, time-resolved infrared spectroscopy, and steady-state photochemical methods. Density functional theory (DFT) was used to assist in the identification of the photoproducts. Irradiation (λ_exc= 406 nm) of (η₅-C₄H₄Se)Cr(CO)₃ in either an Ar or CH₄ matrix at 20 K produced the selenophene ring-opened insertion product (C,Se-C₄H₄Se)Cr(CO)₃. Further irradiation of this matrix produced the CO-loss species (C,Se-C ₄H₄Se)Cr(CO)₂. Pulsed irradiation at 400 nm produced the CO-loss species (η⁵-C₄H ₄Se)Cr(CO)₂(S) in n-heptane (S) along with the insertion products (C,Se-C₄H₄Se)Cr(CO)₃ and (C,Se-C ₄H₄Se)Cr(CO)₂, both of which may have triplet character. Time-resolved measurements on the microsecond time scale confirmed that the CO-loss species (η⁵-C₄H₄Se)Cr(CO) ₂(S) reacts with CO (k₂ = 5.8 × 10⁶ dm³ mol-1 s-1 at 298 K), while (C,Se-C₄H ₄Se)Cr(CO)₃ and (C,Se-C₄H₄Se)Cr(CO) ₂ do not react on this time scale. DFT calculations provide an explanation of the stability of the triplet (C,Se-C₄H ₄Se)Cr(CO)₃ species in terms of a chromaselanabenzene structure, which is consistent with previously observed metal insertion into coordinated selenophene ligands.

Original language	English
Pages (from-to)	3671-3680
Number of pages	10
Journal	Organometallics
Volume	27
Issue number	15
DOIs	https://doi.org/10.1021/om7011979
Publication status	Published - 11 Aug 2008
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{bf66cd6242ff45daa26ac34ef011fb73,

title = "Photoinduced Se-C insertion following photolysis of (η5- C4H4Se)Cr(CO)3. A picosecond and nanosecond time-resolved infrared, matrix isolation, and DFT investigation",

abstract = "The photochemistry of (η5;-C4H 4Se)Cr(CO)3 was investigated by matrix isolation, time-resolved infrared spectroscopy, and steady-state photochemical methods. Density functional theory (DFT) was used to assist in the identification of the photoproducts. Irradiation (λexc= 406 nm) of (η5-C4H4Se)Cr(CO)3 in either an Ar or CH4 matrix at 20 K produced the selenophene ring-opened insertion product (C,Se-C4H4Se)Cr(CO)3. Further irradiation of this matrix produced the CO-loss species (C,Se-C 4H4Se)Cr(CO)2. Pulsed irradiation at 400 nm produced the CO-loss species (η5-C4H 4Se)Cr(CO)2(S) in n-heptane (S) along with the insertion products (C,Se-C4H4Se)Cr(CO)3 and (C,Se-C 4H4Se)Cr(CO)2, both of which may have triplet character. Time-resolved measurements on the microsecond time scale confirmed that the CO-loss species (η5-C4H4Se)Cr(CO) 2(S) reacts with CO (k2 = 5.8 × 106 dm3 mol-1 s-1 at 298 K), while (C,Se-C4H 4Se)Cr(CO)3 and (C,Se-C4H4Se)Cr(CO) 2 do not react on this time scale. DFT calculations provide an explanation of the stability of the triplet (C,Se-C4H 4Se)Cr(CO)3 species in terms of a chromaselanabenzene structure, which is consistent with previously observed metal insertion into coordinated selenophene ligands.",

author = "Peter Brennan and George, {Michael W.} and Jina, {Omar S.} and Conor Long and Jennifer McKenna and Pryce, {Mary T.} and Sun, {Xue Zhong} and Vuong, {Khuong Q.}",

year = "2008",

month = aug,

day = "11",

doi = "10.1021/om7011979",

language = "English",

volume = "27",

pages = "3671--3680",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Photoinduced Se-C insertion following photolysis of (η5- C4H4Se)Cr(CO)3. A picosecond and nanosecond time-resolved infrared, matrix isolation, and DFT investigation

AU - Brennan, Peter

AU - George, Michael W.

AU - Jina, Omar S.

AU - Long, Conor

AU - McKenna, Jennifer

AU - Pryce, Mary T.

AU - Sun, Xue Zhong

AU - Vuong, Khuong Q.

PY - 2008/8/11

Y1 - 2008/8/11

N2 - The photochemistry of (η5;-C4H 4Se)Cr(CO)3 was investigated by matrix isolation, time-resolved infrared spectroscopy, and steady-state photochemical methods. Density functional theory (DFT) was used to assist in the identification of the photoproducts. Irradiation (λexc= 406 nm) of (η5-C4H4Se)Cr(CO)3 in either an Ar or CH4 matrix at 20 K produced the selenophene ring-opened insertion product (C,Se-C4H4Se)Cr(CO)3. Further irradiation of this matrix produced the CO-loss species (C,Se-C 4H4Se)Cr(CO)2. Pulsed irradiation at 400 nm produced the CO-loss species (η5-C4H 4Se)Cr(CO)2(S) in n-heptane (S) along with the insertion products (C,Se-C4H4Se)Cr(CO)3 and (C,Se-C 4H4Se)Cr(CO)2, both of which may have triplet character. Time-resolved measurements on the microsecond time scale confirmed that the CO-loss species (η5-C4H4Se)Cr(CO) 2(S) reacts with CO (k2 = 5.8 × 106 dm3 mol-1 s-1 at 298 K), while (C,Se-C4H 4Se)Cr(CO)3 and (C,Se-C4H4Se)Cr(CO) 2 do not react on this time scale. DFT calculations provide an explanation of the stability of the triplet (C,Se-C4H 4Se)Cr(CO)3 species in terms of a chromaselanabenzene structure, which is consistent with previously observed metal insertion into coordinated selenophene ligands.

AB - The photochemistry of (η5;-C4H 4Se)Cr(CO)3 was investigated by matrix isolation, time-resolved infrared spectroscopy, and steady-state photochemical methods. Density functional theory (DFT) was used to assist in the identification of the photoproducts. Irradiation (λexc= 406 nm) of (η5-C4H4Se)Cr(CO)3 in either an Ar or CH4 matrix at 20 K produced the selenophene ring-opened insertion product (C,Se-C4H4Se)Cr(CO)3. Further irradiation of this matrix produced the CO-loss species (C,Se-C 4H4Se)Cr(CO)2. Pulsed irradiation at 400 nm produced the CO-loss species (η5-C4H 4Se)Cr(CO)2(S) in n-heptane (S) along with the insertion products (C,Se-C4H4Se)Cr(CO)3 and (C,Se-C 4H4Se)Cr(CO)2, both of which may have triplet character. Time-resolved measurements on the microsecond time scale confirmed that the CO-loss species (η5-C4H4Se)Cr(CO) 2(S) reacts with CO (k2 = 5.8 × 106 dm3 mol-1 s-1 at 298 K), while (C,Se-C4H 4Se)Cr(CO)3 and (C,Se-C4H4Se)Cr(CO) 2 do not react on this time scale. DFT calculations provide an explanation of the stability of the triplet (C,Se-C4H 4Se)Cr(CO)3 species in terms of a chromaselanabenzene structure, which is consistent with previously observed metal insertion into coordinated selenophene ligands.

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U2 - 10.1021/om7011979

DO - 10.1021/om7011979

M3 - Article

AN - SCOPUS:50549094156

SN - 0276-7333

VL - 27

SP - 3671

EP - 3680

JO - Organometallics

JF - Organometallics

IS - 15

ER -

Photoinduced Se-C insertion following photolysis of (η⁵- C₄H₄Se)Cr(CO)₃. A picosecond and nanosecond time-resolved infrared, matrix isolation, and DFT investigation

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