Influence of electron-deficient ruthenium(I) carbonyl carboxylates on the vinylogous reactivity of metal carbenoids

Yulia Sevryugina; Beth Weaver; Jørn Hansen; Janelle Thompson; Huw M.L. Davies; Marina A. Petrukhina

doi:10.1021/om700888f

Influence of electron-deficient ruthenium(I) carbonyl carboxylates on the vinylogous reactivity of metal carbenoids

Yulia Sevryugina
, Beth Weaver
, Jørn Hansen
, Janelle Thompson
, Huw M.L. Davies
, Marina A. Petrukhina

Chemistry

University at Albany

SUNY Albany
SUNY Buffalo

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

45 Scopus citations

Abstract

Highly electrophilic ruthenium(I) mixed carbonyl carboxylate complexes exhibit catalytic activity in the cyclopropanation of styrene with methyl phenyldiazoacetate. A particular advantage of these catalysts is their propensity to enhance vinylogous reactivity in the reactions of vinyldiazoacetates. The catalytic study was conducted on four known ruthenium(I) mixed carbonyl carboxylate complexes and four new complexes, namely, [Ru ₂(O₂C(2,3,4-F)₃C₆H₂) ₂(CO)₅], [Ru₂(O₂C(2,4,6-F) ₃C₆H₂)₂(CO)₅], [Ru ₂(O₂CC₆F₅)₂(CO) ₅], and [Ru₂(O₂C(3,5-CF₃) ₂C₆H₃)₂(CO)₄]. All complexes have been prepared by a combination of solvent-free techniques: melt reactions of ruthenium carbonyl with a benzoic acid followed by gas-phase sublimation-deposition of the products under reduced pressure. X-ray crystallographic characterization revealed a tetranuclear "dimer of dimers" type of structure for the [Ru₂(O₂CR) ₂(CO)₅] complexes and a polymeric chain for [Ru ₂(O₂C(3,5-CF₃)₂C₆H ₃)₂(CO)₄]. Both motifs are built on diruthenium(I,I) units linked in the solid state by axial Ru ⋯ O interactions. The solution behavior of the polynuclear ruthenium(I) complexes in solvents of varying coordination ability has been investigated to show a breakage of weak Ru ⋯ O contacts, resulting in the formation of one- and two-end open dimetal units.

Original language	English
Pages (from-to)	1750-1757
Number of pages	8
Journal	Organometallics
Volume	27
Issue number	8
DOIs	https://doi.org/10.1021/om700888f
State	Published - Apr 28 2008

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title = "Influence of electron-deficient ruthenium(I) carbonyl carboxylates on the vinylogous reactivity of metal carbenoids",

abstract = "Highly electrophilic ruthenium(I) mixed carbonyl carboxylate complexes exhibit catalytic activity in the cyclopropanation of styrene with methyl phenyldiazoacetate. A particular advantage of these catalysts is their propensity to enhance vinylogous reactivity in the reactions of vinyldiazoacetates. The catalytic study was conducted on four known ruthenium(I) mixed carbonyl carboxylate complexes and four new complexes, namely, [Ru 2(O2C(2,3,4-F)3C6H2) 2(CO)5], [Ru2(O2C(2,4,6-F) 3C6H2)2(CO)5], [Ru 2(O2CC6F5)2(CO) 5], and [Ru2(O2C(3,5-CF3) 2C6H3)2(CO)4]. All complexes have been prepared by a combination of solvent-free techniques: melt reactions of ruthenium carbonyl with a benzoic acid followed by gas-phase sublimation-deposition of the products under reduced pressure. X-ray crystallographic characterization revealed a tetranuclear {"}dimer of dimers{"} type of structure for the [Ru2(O2CR) 2(CO)5] complexes and a polymeric chain for [Ru 2(O2C(3,5-CF3)2C6H 3)2(CO)4]. Both motifs are built on diruthenium(I,I) units linked in the solid state by axial Ru ⋯ O interactions. The solution behavior of the polynuclear ruthenium(I) complexes in solvents of varying coordination ability has been investigated to show a breakage of weak Ru ⋯ O contacts, resulting in the formation of one- and two-end open dimetal units.",

author = "Yulia Sevryugina and Beth Weaver and J{\o}rn Hansen and Janelle Thompson and Davies, \{Huw M.L.\} and Petrukhina, \{Marina A.\}",

year = "2008",

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doi = "10.1021/om700888f",

language = "English",

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pages = "1750--1757",

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T1 - Influence of electron-deficient ruthenium(I) carbonyl carboxylates on the vinylogous reactivity of metal carbenoids

AU - Sevryugina, Yulia

AU - Weaver, Beth

AU - Hansen, Jørn

AU - Thompson, Janelle

AU - Davies, Huw M.L.

AU - Petrukhina, Marina A.

PY - 2008/4/28

Y1 - 2008/4/28

N2 - Highly electrophilic ruthenium(I) mixed carbonyl carboxylate complexes exhibit catalytic activity in the cyclopropanation of styrene with methyl phenyldiazoacetate. A particular advantage of these catalysts is their propensity to enhance vinylogous reactivity in the reactions of vinyldiazoacetates. The catalytic study was conducted on four known ruthenium(I) mixed carbonyl carboxylate complexes and four new complexes, namely, [Ru 2(O2C(2,3,4-F)3C6H2) 2(CO)5], [Ru2(O2C(2,4,6-F) 3C6H2)2(CO)5], [Ru 2(O2CC6F5)2(CO) 5], and [Ru2(O2C(3,5-CF3) 2C6H3)2(CO)4]. All complexes have been prepared by a combination of solvent-free techniques: melt reactions of ruthenium carbonyl with a benzoic acid followed by gas-phase sublimation-deposition of the products under reduced pressure. X-ray crystallographic characterization revealed a tetranuclear "dimer of dimers" type of structure for the [Ru2(O2CR) 2(CO)5] complexes and a polymeric chain for [Ru 2(O2C(3,5-CF3)2C6H 3)2(CO)4]. Both motifs are built on diruthenium(I,I) units linked in the solid state by axial Ru ⋯ O interactions. The solution behavior of the polynuclear ruthenium(I) complexes in solvents of varying coordination ability has been investigated to show a breakage of weak Ru ⋯ O contacts, resulting in the formation of one- and two-end open dimetal units.

AB - Highly electrophilic ruthenium(I) mixed carbonyl carboxylate complexes exhibit catalytic activity in the cyclopropanation of styrene with methyl phenyldiazoacetate. A particular advantage of these catalysts is their propensity to enhance vinylogous reactivity in the reactions of vinyldiazoacetates. The catalytic study was conducted on four known ruthenium(I) mixed carbonyl carboxylate complexes and four new complexes, namely, [Ru 2(O2C(2,3,4-F)3C6H2) 2(CO)5], [Ru2(O2C(2,4,6-F) 3C6H2)2(CO)5], [Ru 2(O2CC6F5)2(CO) 5], and [Ru2(O2C(3,5-CF3) 2C6H3)2(CO)4]. All complexes have been prepared by a combination of solvent-free techniques: melt reactions of ruthenium carbonyl with a benzoic acid followed by gas-phase sublimation-deposition of the products under reduced pressure. X-ray crystallographic characterization revealed a tetranuclear "dimer of dimers" type of structure for the [Ru2(O2CR) 2(CO)5] complexes and a polymeric chain for [Ru 2(O2C(3,5-CF3)2C6H 3)2(CO)4]. Both motifs are built on diruthenium(I,I) units linked in the solid state by axial Ru ⋯ O interactions. The solution behavior of the polynuclear ruthenium(I) complexes in solvents of varying coordination ability has been investigated to show a breakage of weak Ru ⋯ O contacts, resulting in the formation of one- and two-end open dimetal units.

UR - https://www.scopus.com/pages/publications/43249106770

U2 - 10.1021/om700888f

DO - 10.1021/om700888f

M3 - Article

SN - 0276-7333

VL - 27

SP - 1750

EP - 1757

JO - Organometallics

JF - Organometallics

IS - 8

ER -

Influence of electron-deficient ruthenium(I) carbonyl carboxylates on the vinylogous reactivity of metal carbenoids

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