Products from the photoreaction of (Me3P)(OC)4OsW(CO)5 with CCl4; synthesis and isomerization of Os(CO) 3(PMe3)Cl2

Jonathan L. Male; Frederick W.B. Einstein; Weng K. Leong; Roland K. Pomeroy; David R. Tyler

doi:10.1016/S0022-328X(97)00469-5

Products from the photoreaction of (Me₃P)(OC)₄OsW(CO)₅ with CCl₄; synthesis and isomerization of Os(CO) ₃(PMe₃)Cl₂

Jonathan L. Male, Frederick W.B. Einstein, Weng K. Leong, Roland K. Pomeroy^*, David R. Tyler

^*Corresponding author for this work

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

6 Citations (Scopus)

Abstract

This paper reports the characterization of the fac-Os(CO)₃(PMe₃)Cl₂ (fac-2) product that is formed when (Me₃P)(OC)₄OsW(CO)₅ (1; a complex with a dative Os-W bond) is irradiated (λ > 400 nm) in the presence of CCl₄. In an attempt to independently synthesize fac-2, Os₃(CO)₉(PMe₃)₃ was allowed to react with Cl₂. The product, however, was mer-cis-Os(CO)₃(PMe₃)Cl₂ (mer-cis-2). The mer-cis isomer is converted to the fac isomer (fac-2) by stirring under nitrogen in THF for nine days. The stereochemistry of each compound was confirmed by infrared and NMR spectroscopy and by X-ray crystallography. The [Os(CO)₂(PMe₃)(Cl)(μ-Cl)]₂ compound (3) was also formed as a minor product in the conversion of mer-cis-Os(CO)₃(PMe₃)Cl₂ to fac-Os(CO)₃(PMe₃)Cl₂. Irradiation (λ > 400 nm) of Os(CO)₄(PMe₃) in benzene in the presence of CCl₄ gave a product tentatively identified as fac-Os(CO)₃(PMe₃)(CCl₃)Cl (4), which results from the oxidative-addition of CCl₄ to Os(CO)₃(PMe₃).

Original language	English
Pages (from-to)	105-115
Number of pages	11
Journal	Journal of Organometallic Chemistry
Volume	549
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(97)00469-5
Publication status	Published - Dec 18 1997
Externally published	Yes

ASJC Scopus Subject Areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Keywords

Isomerization
Mer-cis-to fac-isomerization
Oxidative-addition of CCl
Photochemistry

Access to Document

10.1016/S0022-328X(97)00469-5

Cite this

@article{3cc6134628f74e3098e492b979fb050f,

title = "Products from the photoreaction of (Me3P)(OC)4OsW(CO)5 with CCl4; synthesis and isomerization of Os(CO) 3(PMe3)Cl2",

abstract = "This paper reports the characterization of the fac-Os(CO)3(PMe3)Cl2 (fac-2) product that is formed when (Me3P)(OC)4OsW(CO)5 (1; a complex with a dative Os-W bond) is irradiated (λ > 400 nm) in the presence of CCl4. In an attempt to independently synthesize fac-2, Os3(CO)9(PMe3)3 was allowed to react with Cl2. The product, however, was mer-cis-Os(CO)3(PMe3)Cl2 (mer-cis-2). The mer-cis isomer is converted to the fac isomer (fac-2) by stirring under nitrogen in THF for nine days. The stereochemistry of each compound was confirmed by infrared and NMR spectroscopy and by X-ray crystallography. The [Os(CO)2(PMe3)(Cl)(μ-Cl)]2 compound (3) was also formed as a minor product in the conversion of mer-cis-Os(CO)3(PMe3)Cl2 to fac-Os(CO)3(PMe3)Cl2. Irradiation (λ > 400 nm) of Os(CO)4(PMe3) in benzene in the presence of CCl4 gave a product tentatively identified as fac-Os(CO)3(PMe3)(CCl3)Cl (4), which results from the oxidative-addition of CCl4 to Os(CO)3(PMe3).",

keywords = "Isomerization, Mer-cis-to fac-isomerization, Oxidative-addition of CCl, Photochemistry",

author = "Male, {Jonathan L.} and Einstein, {Frederick W.B.} and Leong, {Weng K.} and Pomeroy, {Roland K.} and Tyler, {David R.}",

year = "1997",

month = dec,

day = "18",

doi = "10.1016/S0022-328X(97)00469-5",

language = "English",

volume = "549",

pages = "105--115",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-2",

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TY - JOUR

T1 - Products from the photoreaction of (Me3P)(OC)4OsW(CO)5 with CCl4; synthesis and isomerization of Os(CO) 3(PMe3)Cl2

AU - Male, Jonathan L.

AU - Einstein, Frederick W.B.

AU - Leong, Weng K.

AU - Pomeroy, Roland K.

AU - Tyler, David R.

PY - 1997/12/18

Y1 - 1997/12/18

N2 - This paper reports the characterization of the fac-Os(CO)3(PMe3)Cl2 (fac-2) product that is formed when (Me3P)(OC)4OsW(CO)5 (1; a complex with a dative Os-W bond) is irradiated (λ > 400 nm) in the presence of CCl4. In an attempt to independently synthesize fac-2, Os3(CO)9(PMe3)3 was allowed to react with Cl2. The product, however, was mer-cis-Os(CO)3(PMe3)Cl2 (mer-cis-2). The mer-cis isomer is converted to the fac isomer (fac-2) by stirring under nitrogen in THF for nine days. The stereochemistry of each compound was confirmed by infrared and NMR spectroscopy and by X-ray crystallography. The [Os(CO)2(PMe3)(Cl)(μ-Cl)]2 compound (3) was also formed as a minor product in the conversion of mer-cis-Os(CO)3(PMe3)Cl2 to fac-Os(CO)3(PMe3)Cl2. Irradiation (λ > 400 nm) of Os(CO)4(PMe3) in benzene in the presence of CCl4 gave a product tentatively identified as fac-Os(CO)3(PMe3)(CCl3)Cl (4), which results from the oxidative-addition of CCl4 to Os(CO)3(PMe3).

AB - This paper reports the characterization of the fac-Os(CO)3(PMe3)Cl2 (fac-2) product that is formed when (Me3P)(OC)4OsW(CO)5 (1; a complex with a dative Os-W bond) is irradiated (λ > 400 nm) in the presence of CCl4. In an attempt to independently synthesize fac-2, Os3(CO)9(PMe3)3 was allowed to react with Cl2. The product, however, was mer-cis-Os(CO)3(PMe3)Cl2 (mer-cis-2). The mer-cis isomer is converted to the fac isomer (fac-2) by stirring under nitrogen in THF for nine days. The stereochemistry of each compound was confirmed by infrared and NMR spectroscopy and by X-ray crystallography. The [Os(CO)2(PMe3)(Cl)(μ-Cl)]2 compound (3) was also formed as a minor product in the conversion of mer-cis-Os(CO)3(PMe3)Cl2 to fac-Os(CO)3(PMe3)Cl2. Irradiation (λ > 400 nm) of Os(CO)4(PMe3) in benzene in the presence of CCl4 gave a product tentatively identified as fac-Os(CO)3(PMe3)(CCl3)Cl (4), which results from the oxidative-addition of CCl4 to Os(CO)3(PMe3).

KW - Isomerization

KW - Mer-cis-to fac-isomerization

KW - Oxidative-addition of CCl

KW - Photochemistry

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