Preparation, structures, and haptotropic rearrangement of novel dinuclear ruthenium complexes, (μ235- guaiazulene)Ru2(CO)4(CNR)

Kouki Matsubara, Shoji Mima, Takashi Oda, Hideo Nagashima

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Novel isonitrile derivatives of a diruthenium carbonyl complex, (μ235-guaiazulene)Ru2(CO)5 (2), were synthesized by substitution of a CO ligand by an isonitrile, and were subjected to studies on thermal and photochemical haptotropic interconvension. Treatment of 2 (a 45:55 mixture of two haptotropic isomers. 2-A and 2-B) with RNC at room temperature resulted in coordination of RNC and alternation of the coordination mode of the guaiazulene ligand to form (μ2η15-guaiazulene)Ru2(CO)5(CNR), 5d-5f, [5d; R = 'Bu, 5e; 2,4,6-Me3C6H2, or 5f; 2,6-iPr2C6H3] in moderate to good yields. Thermal dissociation of a CO ligand from 5 at 60 °C resulted in quantitative formation of a desirable isonitrile analogue of 2. (μ235-guaiazulene)Ru2(CO)4(CNR), 4d-4f, [4d; R = 'Bu, 4e; 2,4,6-Me3C6H2, or 4f' 2,6-iPr2H3], as a 1:1 mixture of the two haptotropic isomers. A direct synthetic route from 2 to 4d-4f was alternatively discovered; treatment of 2 with one equivalent of RNC at 60 °C have 4d-4f in moderate yields. All of the new compounds were characterized by spectroscopy, and structures of 5d (R = 'Bu) and 4d-A (R = 'Bu) were determined by crystallography. Thermal and photochemical interconvention between the two haptotropic isomers of 4d-4f revealed that the isomer ratios in the thermal equilibrium and in the photostatic state were in the range of 48:52-54:46.

Original languageEnglish
Pages (from-to)96-107
Number of pages12
JournalJournal of Organometallic Chemistry
Volume650
Issue number1-2
DOIs
Publication statusPublished - May 1 2002

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Ruthenium
Carbon Monoxide
Isomers
ruthenium
isomers
preparation
Hot Temperature
Ligands
ligands
thermal dissociation
Crystallography
alternations
crystallography
Substitution reactions
routes
Spectroscopy
substitutes
analogs
Derivatives
Spectrum Analysis

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Preparation, structures, and haptotropic rearrangement of novel dinuclear ruthenium complexes, (μ235- guaiazulene)Ru2(CO)4(CNR). / Matsubara, Kouki; Mima, Shoji; Oda, Takashi; Nagashima, Hideo.

In: Journal of Organometallic Chemistry, Vol. 650, No. 1-2, 01.05.2002, p. 96-107.

Research output: Contribution to journalArticle

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abstract = "Novel isonitrile derivatives of a diruthenium carbonyl complex, (μ2.η3:η5-guaiazulene)Ru2(CO)5 (2), were synthesized by substitution of a CO ligand by an isonitrile, and were subjected to studies on thermal and photochemical haptotropic interconvension. Treatment of 2 (a 45:55 mixture of two haptotropic isomers. 2-A and 2-B) with RNC at room temperature resulted in coordination of RNC and alternation of the coordination mode of the guaiazulene ligand to form (μ2η1:η5-guaiazulene)Ru2(CO)5(CNR), 5d-5f, [5d; R = 'Bu, 5e; 2,4,6-Me3C6H2, or 5f; 2,6-iPr2C6H3] in moderate to good yields. Thermal dissociation of a CO ligand from 5 at 60 °C resulted in quantitative formation of a desirable isonitrile analogue of 2. (μ2.η3:η5-guaiazulene)Ru2(CO)4(CNR), 4d-4f, [4d; R = 'Bu, 4e; 2,4,6-Me3C6H2, or 4f' 2,6-iPr2H3], as a 1:1 mixture of the two haptotropic isomers. A direct synthetic route from 2 to 4d-4f was alternatively discovered; treatment of 2 with one equivalent of RNC at 60 °C have 4d-4f in moderate yields. All of the new compounds were characterized by spectroscopy, and structures of 5d (R = 'Bu) and 4d-A (R = 'Bu) were determined by crystallography. Thermal and photochemical interconvention between the two haptotropic isomers of 4d-4f revealed that the isomer ratios in the thermal equilibrium and in the photostatic state were in the range of 48:52-54:46.",
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N2 - Novel isonitrile derivatives of a diruthenium carbonyl complex, (μ2.η3:η5-guaiazulene)Ru2(CO)5 (2), were synthesized by substitution of a CO ligand by an isonitrile, and were subjected to studies on thermal and photochemical haptotropic interconvension. Treatment of 2 (a 45:55 mixture of two haptotropic isomers. 2-A and 2-B) with RNC at room temperature resulted in coordination of RNC and alternation of the coordination mode of the guaiazulene ligand to form (μ2η1:η5-guaiazulene)Ru2(CO)5(CNR), 5d-5f, [5d; R = 'Bu, 5e; 2,4,6-Me3C6H2, or 5f; 2,6-iPr2C6H3] in moderate to good yields. Thermal dissociation of a CO ligand from 5 at 60 °C resulted in quantitative formation of a desirable isonitrile analogue of 2. (μ2.η3:η5-guaiazulene)Ru2(CO)4(CNR), 4d-4f, [4d; R = 'Bu, 4e; 2,4,6-Me3C6H2, or 4f' 2,6-iPr2H3], as a 1:1 mixture of the two haptotropic isomers. A direct synthetic route from 2 to 4d-4f was alternatively discovered; treatment of 2 with one equivalent of RNC at 60 °C have 4d-4f in moderate yields. All of the new compounds were characterized by spectroscopy, and structures of 5d (R = 'Bu) and 4d-A (R = 'Bu) were determined by crystallography. Thermal and photochemical interconvention between the two haptotropic isomers of 4d-4f revealed that the isomer ratios in the thermal equilibrium and in the photostatic state were in the range of 48:52-54:46.

AB - Novel isonitrile derivatives of a diruthenium carbonyl complex, (μ2.η3:η5-guaiazulene)Ru2(CO)5 (2), were synthesized by substitution of a CO ligand by an isonitrile, and were subjected to studies on thermal and photochemical haptotropic interconvension. Treatment of 2 (a 45:55 mixture of two haptotropic isomers. 2-A and 2-B) with RNC at room temperature resulted in coordination of RNC and alternation of the coordination mode of the guaiazulene ligand to form (μ2η1:η5-guaiazulene)Ru2(CO)5(CNR), 5d-5f, [5d; R = 'Bu, 5e; 2,4,6-Me3C6H2, or 5f; 2,6-iPr2C6H3] in moderate to good yields. Thermal dissociation of a CO ligand from 5 at 60 °C resulted in quantitative formation of a desirable isonitrile analogue of 2. (μ2.η3:η5-guaiazulene)Ru2(CO)4(CNR), 4d-4f, [4d; R = 'Bu, 4e; 2,4,6-Me3C6H2, or 4f' 2,6-iPr2H3], as a 1:1 mixture of the two haptotropic isomers. A direct synthetic route from 2 to 4d-4f was alternatively discovered; treatment of 2 with one equivalent of RNC at 60 °C have 4d-4f in moderate yields. All of the new compounds were characterized by spectroscopy, and structures of 5d (R = 'Bu) and 4d-A (R = 'Bu) were determined by crystallography. Thermal and photochemical interconvention between the two haptotropic isomers of 4d-4f revealed that the isomer ratios in the thermal equilibrium and in the photostatic state were in the range of 48:52-54:46.

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