Preparation and Reactions of [CpOs(CH3CN)3]+. A Useful Synthetic Intermediate for the Preparation of CpOsL3 Compounds

Daniel A. Freedman; Thomas P. Gill; Amy M. Blough; Robert S. Koefod; Kent R. Mann

doi:10.1021/ic9601504

Preparation and Reactions of [CpOs(CH₃CN)₃]⁺. A Useful Synthetic Intermediate for the Preparation of CpOsL₃ Compounds

Daniel A. Freedman, Thomas P. Gill, Amy M. Blough, Robert S. Koefod, Kent R. Mann

Chemistry (Twin Cities)

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Abstract

A photochemical synthesis of [CpOs(CH₃CN)₃]⁺ is reported (Cp = η⁵-cyclopentadienyl). Photolysis of [CpOs(Bz)]⁺ (Bz = η⁶-benzene) in acetonitrile solution gives [CpOs(CH₃CN)₃]⁺, but only 30% conversion is achieved before significant photochemically induced decomposition of [CpOs(CH₃CN)₃]⁺ occurs. Photolysis of acetonitrile solutions of [CpOs(Bz)]⁺ that contain biphenyl eliminates this side reaction and allows the high-yield preparation of [CpOs(CH₃CN)₃]⁺. Quantum yields for the photodearylation reaction are identical in the presence or absence of biphenyl, suggesting that biphenyl acts as a passive filter, slowing the photochemical decomposition of [CpOs(CH₃CN)₃]⁺, [CpOs(CH₃CN)₃]⁺ reacts with arenes, CO, and polypyrazolylborate ligands, providing a high-yield route to CpOsL₃ compounds under mild conditions. Compounds that were synthesized and fully characterized include [CpOs(η⁶-anthracene)]PF₆. [CpOs(η⁶-rubrene)]PF₆, CpOs(BPz₄) (BPz₄^- = tetrakis(1-pyrazolyl)borate), CpOs(HBPz₃) (HBPz₃ = hydrotris(1-pyrazolyl)borate), [CpOs(CH₃CN)₂CO]PF₆, and CpOs(CO)₂Br. ¹H NMR evidence for an additional species ([(CpOs)(CpOs(CH₃CN))(μ-η⁶, η⁴-anth)]²⁺) that contains an η⁶ and an η⁴ CpOs⁺ group is presented. Intriguing differences between the reactivity of [CpOs(CH₃CN)₃]⁺ and [CpRu(CH₃CN)₃]⁺ with rubrene are observed, with the osmium complex showing a remarkable kinetic preference for the naphthacene backbone relative to the pendant phenyl rings.

Original language	English (US)
Pages (from-to)	95-102
Number of pages	8
Journal	Inorganic chemistry
Volume	36
Issue number	1
DOIs	https://doi.org/10.1021/ic9601504
State	Published - 1997

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@article{5654811cc46341008316fca48fe59a39,

title = "Preparation and Reactions of [CpOs(CH3CN)3]+. A Useful Synthetic Intermediate for the Preparation of CpOsL3 Compounds",

abstract = "A photochemical synthesis of [CpOs(CH3CN)3]+ is reported (Cp = η5-cyclopentadienyl). Photolysis of [CpOs(Bz)]+ (Bz = η6-benzene) in acetonitrile solution gives [CpOs(CH3CN)3]+, but only 30% conversion is achieved before significant photochemically induced decomposition of [CpOs(CH3CN)3]+ occurs. Photolysis of acetonitrile solutions of [CpOs(Bz)]+ that contain biphenyl eliminates this side reaction and allows the high-yield preparation of [CpOs(CH3CN)3]+. Quantum yields for the photodearylation reaction are identical in the presence or absence of biphenyl, suggesting that biphenyl acts as a passive filter, slowing the photochemical decomposition of [CpOs(CH3CN)3]+, [CpOs(CH3CN)3]+ reacts with arenes, CO, and polypyrazolylborate ligands, providing a high-yield route to CpOsL3 compounds under mild conditions. Compounds that were synthesized and fully characterized include [CpOs(η6-anthracene)]PF6. [CpOs(η6-rubrene)]PF6, CpOs(BPz4) (BPz4- = tetrakis(1-pyrazolyl)borate), CpOs(HBPz3) (HBPz3 = hydrotris(1-pyrazolyl)borate), [CpOs(CH3CN)2CO]PF6, and CpOs(CO)2Br. 1H NMR evidence for an additional species ([(CpOs)(CpOs(CH3CN))(μ-η6, η4-anth)]2+) that contains an η6 and an η4 CpOs+ group is presented. Intriguing differences between the reactivity of [CpOs(CH3CN)3]+ and [CpRu(CH3CN)3]+ with rubrene are observed, with the osmium complex showing a remarkable kinetic preference for the naphthacene backbone relative to the pendant phenyl rings.",

author = "Freedman, {Daniel A.} and Gill, {Thomas P.} and Blough, {Amy M.} and Koefod, {Robert S.} and Mann, {Kent R.}",

year = "1997",

doi = "10.1021/ic9601504",

language = "English (US)",

volume = "36",

pages = "95--102",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "1",

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T1 - Preparation and Reactions of [CpOs(CH3CN)3]+. A Useful Synthetic Intermediate for the Preparation of CpOsL3 Compounds

AU - Freedman, Daniel A.

AU - Gill, Thomas P.

AU - Blough, Amy M.

AU - Koefod, Robert S.

AU - Mann, Kent R.

PY - 1997

Y1 - 1997

N2 - A photochemical synthesis of [CpOs(CH3CN)3]+ is reported (Cp = η5-cyclopentadienyl). Photolysis of [CpOs(Bz)]+ (Bz = η6-benzene) in acetonitrile solution gives [CpOs(CH3CN)3]+, but only 30% conversion is achieved before significant photochemically induced decomposition of [CpOs(CH3CN)3]+ occurs. Photolysis of acetonitrile solutions of [CpOs(Bz)]+ that contain biphenyl eliminates this side reaction and allows the high-yield preparation of [CpOs(CH3CN)3]+. Quantum yields for the photodearylation reaction are identical in the presence or absence of biphenyl, suggesting that biphenyl acts as a passive filter, slowing the photochemical decomposition of [CpOs(CH3CN)3]+, [CpOs(CH3CN)3]+ reacts with arenes, CO, and polypyrazolylborate ligands, providing a high-yield route to CpOsL3 compounds under mild conditions. Compounds that were synthesized and fully characterized include [CpOs(η6-anthracene)]PF6. [CpOs(η6-rubrene)]PF6, CpOs(BPz4) (BPz4- = tetrakis(1-pyrazolyl)borate), CpOs(HBPz3) (HBPz3 = hydrotris(1-pyrazolyl)borate), [CpOs(CH3CN)2CO]PF6, and CpOs(CO)2Br. 1H NMR evidence for an additional species ([(CpOs)(CpOs(CH3CN))(μ-η6, η4-anth)]2+) that contains an η6 and an η4 CpOs+ group is presented. Intriguing differences between the reactivity of [CpOs(CH3CN)3]+ and [CpRu(CH3CN)3]+ with rubrene are observed, with the osmium complex showing a remarkable kinetic preference for the naphthacene backbone relative to the pendant phenyl rings.

AB - A photochemical synthesis of [CpOs(CH3CN)3]+ is reported (Cp = η5-cyclopentadienyl). Photolysis of [CpOs(Bz)]+ (Bz = η6-benzene) in acetonitrile solution gives [CpOs(CH3CN)3]+, but only 30% conversion is achieved before significant photochemically induced decomposition of [CpOs(CH3CN)3]+ occurs. Photolysis of acetonitrile solutions of [CpOs(Bz)]+ that contain biphenyl eliminates this side reaction and allows the high-yield preparation of [CpOs(CH3CN)3]+. Quantum yields for the photodearylation reaction are identical in the presence or absence of biphenyl, suggesting that biphenyl acts as a passive filter, slowing the photochemical decomposition of [CpOs(CH3CN)3]+, [CpOs(CH3CN)3]+ reacts with arenes, CO, and polypyrazolylborate ligands, providing a high-yield route to CpOsL3 compounds under mild conditions. Compounds that were synthesized and fully characterized include [CpOs(η6-anthracene)]PF6. [CpOs(η6-rubrene)]PF6, CpOs(BPz4) (BPz4- = tetrakis(1-pyrazolyl)borate), CpOs(HBPz3) (HBPz3 = hydrotris(1-pyrazolyl)borate), [CpOs(CH3CN)2CO]PF6, and CpOs(CO)2Br. 1H NMR evidence for an additional species ([(CpOs)(CpOs(CH3CN))(μ-η6, η4-anth)]2+) that contains an η6 and an η4 CpOs+ group is presented. Intriguing differences between the reactivity of [CpOs(CH3CN)3]+ and [CpRu(CH3CN)3]+ with rubrene are observed, with the osmium complex showing a remarkable kinetic preference for the naphthacene backbone relative to the pendant phenyl rings.

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Preparation and Reactions of [CpOs(CH₃CN)₃]⁺. A Useful Synthetic Intermediate for the Preparation of CpOsL₃ Compounds

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