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Substituent effect on reactions of ReH 5 (PMe 2 Ph) 3 with propargyl alcohols

Inorganica Chimica Acta, ISSN: 0020-1693, Vol: 518, Page: 120239
2021
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Reactions of the rhenium polyhydride ReH 5 (PMe 2 Ph) 3 with propargyl alcohols in the presence of HCl can produce γ-hydroxycarbyne, vinylcarbyne and η 2 -vinyl complexes, the relative amounts of which are dependent on the substituents of the propargyl alcohols. The reaction with the bis- alkyl substituted propargyl alcohol HC CC(OH)Me 2 produced only the vinylcarbyne complex ReCl 2 (≡CCH=CMe 2 )(PMe 2 Ph) 3. The reaction with the bis- alkynyl substituted propargyl alcohol HC CC(OH)(C CSiMe 3 ) 2 produced only the η 2 -vinyl complex ReCl 2 { η 2 -CH 2 =CC(OH)(C CSiMe 3 ) 2 }(PMe 2 Ph) 3. The reactions with the bis- ( o -functionalized aryl) substituted propargyl alcohols HC CC(OH)Ar 2 (Ar =  o -C 6 H 4 Br, o, o' -C 6 H 3 Cl 2 ) produced only the γ-hydroxycarbyne complexes Re{≡CCH 2 C(OH)Ar 2 }Cl 2 (PMe 2 Ph) 3. The reactions with the monoaryl substituted propargyl alcohol HC CC(OH)Ph(C CSiMe 3 ) produced a mixture of the vinylcarbyne Re{≡CCH=CPh(C CSiMe 3 )}Cl 2 (PMe 2 Ph) 3, the γ-hydroxycarbyne Re{≡CCH 2 C(OH)Ph(C CSiMe 3 )}Cl 2 (PMe 2 Ph) 3 and the η 2 -vinyl complex Re{η 2 -CH 2 =CC(OH)Ph(C CSiMe 3 )}Cl 2 (PMe 2 Ph) 3. The selectivity for the products can be related to the steric and electronic effect of the substituents of propargyl alcohols. In general, formation of η 2 -vinyl complexes is favored over carbyne complexes when the substituents are sterically less demanding. Formation of γ-hydroxycarbyne complexes is favored over vinylcarbyne complexes when the substituents are electron withdrawing.

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