Solution and nujol matrix photochemistry of (η5-C5H5)2Os 2(CO)4 and nujol matrix photochemistry of (η5-C5H4CH3)2Ru 2(CO)4 and (η5-C5H5)M(CO)2H, where M = Ru and Os

Thomas E. Bitterwolf, John Linehan, Joyce E. Shade

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

Lowering the temperature of a Nujol solution of (η5-C5H5CH3Ru 2(CO)4 containing bands of the trans- and cis-bridging and trans-nonbridging isomers from room temperature to ca. 90 K results in complete disappearance of the bands of the trans-terminal isomer. The photochemistry of (η5-C5H4CH3)2Ru 2(CO)4 in frozen Nujol at 90 K differs subtly from that of (η5-C5H5)2Ru 2(CO)4 in inert gas matrixes at 12 K in that the trans-bridging isomer is found to undergo photolysis at high energy (λirr > 250 nm) to yield both the triply bridged carbonyl-loss species, (η5-C5H4CH3)2Ru 2(μ-CO)3, and the cis-bridged species isomer. There is no evidence for formation of the trans-nonbridged isomer upon photolysis as observed for (η5C5H5)2Ru2(CO) 4. The solution photochemistry of (η5-C5H5)2Os 2(CO)4 is shown to closely parallel that of (η5-C5H5)2Ru 2(CO)4. Photolysis of (η5-C5H5)2Os 2(CO)4 in CHCl3 yields (eta;5C5H5)Os(CO)2Cl, while photolysis in benzene yields hydride products believed to arise from metal-to-ring coupling of radicals. Photolysis of (η5-C5H5)2Os 2(CO)4, which exists only in a nonbridged form, in frozen Nujol (90 K) results in CO loss and formation of (η5-C5H5)2Os 2(μ-CO)3 as the only photoproduct. Photolysis of (η5-C5H5M(CO)2H, where M = Ru or Os, in frozen Nujol yields (η5-C5H5)M(CO)H and a second product that appears to be either (η5C5H6)M(CO)2 or the (η5-C5H5)M(CO)2 radical.

Original languageEnglish
Pages (from-to)775-781
Number of pages7
JournalOrganometallics
Volume20
Issue number4
Publication statusPublished - 2001

Fingerprint

Photochemical reactions
Photolysis
photochemical reactions
photolysis
Isomers
isomers
matrices
Noble Gases
products
Benzene
Hydrides
hydrides
rare gases
Metals
benzene
Temperature
rings
room temperature
metals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Solution and nujol matrix photochemistry of (η5-C5H5)2Os 2(CO)4 and nujol matrix photochemistry of (η5-C5H4CH3)2Ru 2(CO)4 and (η5-C5H5)M(CO)2H, where M = Ru and Os. / Bitterwolf, Thomas E.; Linehan, John; Shade, Joyce E.

In: Organometallics, Vol. 20, No. 4, 2001, p. 775-781.

Research output: Contribution to journalArticle

@article{e7f23c7e2ceb497d91ccf5664824496f,
title = "Solution and nujol matrix photochemistry of (η5-C5H5)2Os 2(CO)4 and nujol matrix photochemistry of (η5-C5H4CH3)2Ru 2(CO)4 and (η5-C5H5)M(CO)2H, where M = Ru and Os",
abstract = "Lowering the temperature of a Nujol solution of (η5-C5H5CH3Ru 2(CO)4 containing bands of the trans- and cis-bridging and trans-nonbridging isomers from room temperature to ca. 90 K results in complete disappearance of the bands of the trans-terminal isomer. The photochemistry of (η5-C5H4CH3)2Ru 2(CO)4 in frozen Nujol at 90 K differs subtly from that of (η5-C5H5)2Ru 2(CO)4 in inert gas matrixes at 12 K in that the trans-bridging isomer is found to undergo photolysis at high energy (λirr > 250 nm) to yield both the triply bridged carbonyl-loss species, (η5-C5H4CH3)2Ru 2(μ-CO)3, and the cis-bridged species isomer. There is no evidence for formation of the trans-nonbridged isomer upon photolysis as observed for (η5C5H5)2Ru2(CO) 4. The solution photochemistry of (η5-C5H5)2Os 2(CO)4 is shown to closely parallel that of (η5-C5H5)2Ru 2(CO)4. Photolysis of (η5-C5H5)2Os 2(CO)4 in CHCl3 yields (eta;5C5H5)Os(CO)2Cl, while photolysis in benzene yields hydride products believed to arise from metal-to-ring coupling of radicals. Photolysis of (η5-C5H5)2Os 2(CO)4, which exists only in a nonbridged form, in frozen Nujol (90 K) results in CO loss and formation of (η5-C5H5)2Os 2(μ-CO)3 as the only photoproduct. Photolysis of (η5-C5H5M(CO)2H, where M = Ru or Os, in frozen Nujol yields (η5-C5H5)M(CO)H and a second product that appears to be either (η5C5H6)M(CO)2 or the (η5-C5H5)M(CO)2 radical.",
author = "Bitterwolf, {Thomas E.} and John Linehan and Shade, {Joyce E.}",
year = "2001",
language = "English",
volume = "20",
pages = "775--781",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Solution and nujol matrix photochemistry of (η5-C5H5)2Os 2(CO)4 and nujol matrix photochemistry of (η5-C5H4CH3)2Ru 2(CO)4 and (η5-C5H5)M(CO)2H, where M = Ru and Os

AU - Bitterwolf, Thomas E.

AU - Linehan, John

AU - Shade, Joyce E.

PY - 2001

Y1 - 2001

N2 - Lowering the temperature of a Nujol solution of (η5-C5H5CH3Ru 2(CO)4 containing bands of the trans- and cis-bridging and trans-nonbridging isomers from room temperature to ca. 90 K results in complete disappearance of the bands of the trans-terminal isomer. The photochemistry of (η5-C5H4CH3)2Ru 2(CO)4 in frozen Nujol at 90 K differs subtly from that of (η5-C5H5)2Ru 2(CO)4 in inert gas matrixes at 12 K in that the trans-bridging isomer is found to undergo photolysis at high energy (λirr > 250 nm) to yield both the triply bridged carbonyl-loss species, (η5-C5H4CH3)2Ru 2(μ-CO)3, and the cis-bridged species isomer. There is no evidence for formation of the trans-nonbridged isomer upon photolysis as observed for (η5C5H5)2Ru2(CO) 4. The solution photochemistry of (η5-C5H5)2Os 2(CO)4 is shown to closely parallel that of (η5-C5H5)2Ru 2(CO)4. Photolysis of (η5-C5H5)2Os 2(CO)4 in CHCl3 yields (eta;5C5H5)Os(CO)2Cl, while photolysis in benzene yields hydride products believed to arise from metal-to-ring coupling of radicals. Photolysis of (η5-C5H5)2Os 2(CO)4, which exists only in a nonbridged form, in frozen Nujol (90 K) results in CO loss and formation of (η5-C5H5)2Os 2(μ-CO)3 as the only photoproduct. Photolysis of (η5-C5H5M(CO)2H, where M = Ru or Os, in frozen Nujol yields (η5-C5H5)M(CO)H and a second product that appears to be either (η5C5H6)M(CO)2 or the (η5-C5H5)M(CO)2 radical.

AB - Lowering the temperature of a Nujol solution of (η5-C5H5CH3Ru 2(CO)4 containing bands of the trans- and cis-bridging and trans-nonbridging isomers from room temperature to ca. 90 K results in complete disappearance of the bands of the trans-terminal isomer. The photochemistry of (η5-C5H4CH3)2Ru 2(CO)4 in frozen Nujol at 90 K differs subtly from that of (η5-C5H5)2Ru 2(CO)4 in inert gas matrixes at 12 K in that the trans-bridging isomer is found to undergo photolysis at high energy (λirr > 250 nm) to yield both the triply bridged carbonyl-loss species, (η5-C5H4CH3)2Ru 2(μ-CO)3, and the cis-bridged species isomer. There is no evidence for formation of the trans-nonbridged isomer upon photolysis as observed for (η5C5H5)2Ru2(CO) 4. The solution photochemistry of (η5-C5H5)2Os 2(CO)4 is shown to closely parallel that of (η5-C5H5)2Ru 2(CO)4. Photolysis of (η5-C5H5)2Os 2(CO)4 in CHCl3 yields (eta;5C5H5)Os(CO)2Cl, while photolysis in benzene yields hydride products believed to arise from metal-to-ring coupling of radicals. Photolysis of (η5-C5H5)2Os 2(CO)4, which exists only in a nonbridged form, in frozen Nujol (90 K) results in CO loss and formation of (η5-C5H5)2Os 2(μ-CO)3 as the only photoproduct. Photolysis of (η5-C5H5M(CO)2H, where M = Ru or Os, in frozen Nujol yields (η5-C5H5)M(CO)H and a second product that appears to be either (η5C5H6)M(CO)2 or the (η5-C5H5)M(CO)2 radical.

UR - http://www.scopus.com/inward/record.url?scp=0035250121&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035250121&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0035250121

VL - 20

SP - 775

EP - 781

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 4

ER -