Cycloaddition Reactions of (η6-Tropone)tricarbonylmetal(0) Complexes of Group 6 Metals with Alkynes

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Title:Cycloaddition Reactions of (η6-Tropone)tricarbonylmetal(0) Complexes of Group 6 Metals with Alkynes
Creators:
Morkan, Izzet Amour
Morkan, Ayşe Uztetik
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 11, pp. 1635-1646
Uncontrolled Keywords:Bicyclo[4.2.1]nona-3,5,8-trien-1-ones, Tropone, Photochemical synthesis, Alkynes, Chromium complexes, [6+2] Cycloadditions, Molybdenum complexes

Abstract

(η<sup>6</sup>-Cyclohepta-2,4,6-trien-1-one)tricarbonylmetal(0) complexes of chromium (<strong>2a</strong>), molybdenum (<strong>2b</strong>), and tungsten (<strong>2c</strong>) are formed when tris(acetonitrile)tricarbonylchromium(0), -molybdenum(0), and -tungsten(0), respectively, are treated photochemically with tropone (cyclohepta-2,4,6-trien-1-one) <strong>1</strong>. UV photolysis of <strong>2a</strong>-<strong>2c</strong> and RC≡CR' (R = R' = Ph, Me<sub>3</sub>Si, Et; R = Ph, R' = Me<sub>3</sub>Si) in toluene gives the [6+2] cycloadducts, (η<sup>4</sup>,η<sup>2</sup>-8,9-diphenylbicyclo[4.2.1]nona-3,5,8-trien-1-one)tricarbonylmetal(0) <strong>3a</strong>-<strong>3c</strong>, (η<sup>4</sup>,η<sup>2</sup>-8,9-bis(trimethylsilyl)bicyclo[4.2.1]nona-3,5,8-trien-1-one)tricarbonylmetal(0) <strong>4a</strong>-<strong>4c</strong>, (η<sup>4</sup>,η<sup>2</sup>-8,9-diethylbicyclo[4.2.1]nona-3,5,8-trien-1-one)tricarbonylmetal(0) <strong>5a</strong>-<strong>5c</strong>, and (η<sup>4</sup>,η<sup>2</sup>-8-phenyl-9-(trimethylsilyl)bicyclo[4.2.1]nona-3,5,8-trien-1-one)tricarbonylmetal(0) <strong>6a</strong>-<strong>6c</strong>. Compounds <strong>2a</strong>-<strong>2c</strong>, <strong>3a</strong>-<strong>3c</strong>, <strong>4a</strong>-<strong>4c</strong>, <strong>5a</strong>-<strong>5c</strong>, and <strong>6a</strong>-<strong>6c</strong> were purified by chromatography, recrystallized and isolated as analytically pure crystalline solids in moderate yields and characterized by mass, IR, and NMR spectroscopy. Pure organic heterobicyclotriene ligands <strong>7a</strong>, <strong>8a</strong>, <strong>9a</strong>, and <strong>10a</strong> were isolated from <strong>3a</strong>, <strong>4a</strong>, <strong>5a</strong>, and <strong>6a</strong>, respectively, by treatment with cerium(IV) ammonium nitrate (R = R' = Me<sub>3</sub>Si;<sub> </sub>R = Ph, R' = Me<sub>3</sub>Si) or by heating in toluene (R = R' = Ph, Et). It was not possible to isolate the bicyclic complexes resulting from the reactions of <strong>2a</strong>-<strong>2c</strong> with terminal alkynes like phenylacetylene. <p>

Title:Cycloaddition Reactions of (η6-Tropone)tricarbonylmetal(0) Complexes of Group 6 Metals with Alkynes
Creators:
Morkan, Izzet Amour
Morkan, Ayşe Uztetik
Uncontrolled Keywords:Bicyclo[4.2.1]nona-3,5,8-trien-1-ones, Tropone, Photochemical synthesis, Alkynes, Chromium complexes, [6+2] Cycloadditions, Molybdenum complexes
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:67
Number:11
Page Range:pp. 1635-1646
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20021635UNSPECIFIED
ID Code:2022
Item Type:Article
Deposited On:06 Feb 2009 17:14
Last Modified:06 Feb 2009 16:14

Citation

Morkan, Izzet Amour; Morkan, Ayşe Uztetik (2002) Cycloaddition Reactions of (η6-Tropone)tricarbonylmetal(0) Complexes of Group 6 Metals with Alkynes. Collection of Czechoslovak Chemical Communications, 67 (11). pp. 1635-1646. ISSN 0010-0765

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