Migratory insertion of isocyanide into a ketenyl-tungsten bond as key step in cyclization reactions.

ABSTRACT: Treatment of the side-on tungsten alkyne complex of ethinylethyl ether [Tp*W(CO)₂(η²-C,C'-HCCOCH₂CH₃)]⁺ {Tp* = hydridotris(3,4,5-trimethylpyrazolyl)borate} (2a) with n-Bu₄NI afforded the end-on ketenyl complex [Tp*W(CO)₂(κ¹-HCCO)] (4a). This formal 16 ve complex bearing the prototype of a ketenyl ligand is surprisingly stable and converts only under activation by UV light or heat to form a dinuclear complex [Tp*₂W₂(CO)₄(μ-CCH₂)] (6). The ketenyl ligand in complex 4a underwent a metal template controlled cyclization reaction upon addition of isocyanides. The oxametallacycles [Tp*W(CO)₂{κ²-C,O-C(NHXy)C(H)C

SUBMITTER: Timmermann C 

PROVIDER: S-EPMC8694283 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature