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Keywords:

  • cyclization;
  • hydride ligands;
  • metallacycles;
  • osmium;
  • vinylidene ligands

Abstract

Osmium hydrido vinylidene 1 shows diverse cyclization reactivity with activated terminal alkynes. Treatment of 1 with HC[TRIPLE BOND]CCOR′ (R′=OEt and Me) gave osmafurans 3 a and 3 b via osmium alkenyl/vinylidenes 2 a and 2 b. In addition, 1 reacted with HC[TRIPLE BOND]CCH(OH)C[TRIPLE BOND]CH to yield osmabenzene 4, in which the alkynol acted as a C5 fragment to cyclize with 1. Mechanistic analysis indicates that these reactions and the previous formal [3+3] cycloadditions between 1 and HC[TRIPLE BOND]CCH(OH)R (R=Ph, Et, and vinyl) or HC[TRIPLE BOND]CCH(OEt)2 all go through similar osmabutadiene intermediates. Subsequently, the intermediates either took a “coordination and cyclization” process or a “carbon–carbon coupling” path to cyclization, depending on the coordination ability of substituents on the terminal alkenyl carbon atom.

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Featured Compounds

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  1. 1 - 9
Compound 1
Molecular Weight:1074.03
Molecular Formula:C56H47Cl2OsP3
InChIKey:NUPVHSPNJMMPSU-UHFFFAOYSA-L
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Compound 2a
Molecular Weight:1172.13
Molecular Formula:C61H53Cl2O2OsP3
InChIKey:VCBUHKFRPIFOHS-UHFFFAOYSA-L
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Compound 2b
Molecular Weight:1142.1
Molecular Formula:C60H51Cl2OOsP3
InChIKey:DEERDILFUJWZAX-UHFFFAOYSA-L
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Compound 3a
Molecular Weight:1223.48
Molecular Formula:C61H53BClF4O2OsP3
InChIKey:YKLZSKARYFVTBN-UHFFFAOYSA-M
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Compound 3b
Molecular Weight:1193.46
Molecular Formula:C60H51BClF4OOsP3
InChIKey:LHJAYSCVCJQGGT-UHFFFAOYSA-M
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Compound I
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound II
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 4
Molecular Weight:1398.38
Molecular Formula:C79H64Cl2OsP4
InChIKey:LIQOMLQCALUJAB-GLBXCCPGSA-L
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Compound 4′
Molecular Weight:1682.16
Molecular Formula:C103H84BClOsP4
InChIKey:NEUXRVVLTRRYAP-XFHUIMFHSA-M
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