%0 Journal Article %A Kownacki, Ireneusz %A Orwat, Bartosz %A Marciniec, Bogdan %D 2014 %T Iridium-Promoted Conversion of Chlorosilanes to Alkynyl Derivatives in a One-Pot Reaction Sequence %U https://acs.figshare.com/articles/journal_contribution/Iridium_Promoted_Conversion_of_Chlorosilanes_to_Alkynyl_Derivatives_in_a_One_Pot_Reaction_Sequence/2280741 %R 10.1021/om500320t.s001 %2 https://acs.figshare.com/ndownloader/files/3917142 %K iodosilane molecules %K silylative %K SiR 1nCl %K NMR studies %K terminal alkyne %K equimolar reaction %K Alkynyl Derivatives %K iridium center %K conversion %K oxidative addition %K chlorosilane %X By making use of the catalytic potential of the iridium system [{Ir­(μ-Cl)­(CO)2}2]/NEt­(i-Pr)2 in the synthesis of silyl-functionalized alkynes via silylative coupling of terminal alkynes/diynes with iodosilanes, we propose a new protocol allowing employment of various mono- and dichlorosilanes as reagents. The process is based on a sequence of two reactions occurring simultaneously: i.e., conversion of initial chlorosilane (SiR1nCl4–n) to the appropriate iodosilane via Cl/I nucleophilic substitution and its further conversion to a silylalkyne derivative ((SiR1n(CCR2)4–n) via iridium-catalyzed silylative coupling with terminal alkyne. Under optimum conditions, the method has proved to be effective and versatile in the conversion of a wide range of chlorosilanes to a rich portfolio of various corresponding alkynyl-functionalized silicon derivatives. Additionally, NMR studies of the equimolar reaction of a well-defined iridium­(I) alkynyl precursor with Me3Si–I revealed that Si–I bond activation in iodosilane molecules occurred via oxidative addition to the iridium center. %I ACS Publications