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Trimethylsilyldiazomethane Disassembly at a Three-Fold Symmetric Iron Site.

Authors :: Chivington AD
Squire S
Yamamoto N
Pink M
Griffith MD
Fletcher J
Gao Y
Zadrozny JM
Smith JM
Source :: Inorganic chemistry [Inorg Chem] 2024 Jun 03; Vol. 63 (22), pp. 10221-10229. Date of Electronic Publication: 2024 May 23.
Publication Year :: 2024
Abstract: The reaction of equimolar trimethylsilyldiazomethyllithium (LiTMSD) with high spin ( S = 2) PhB(AdIm) <subscript>3</subscript> FeCl (PhB(AdIm) <subscript>3</subscript> <superscript>-</superscript> = tris(3-adamantylimidazol-2-ylidene)phenylborate) affords the corresponding N- nitrilimido complex PhB(AdIm) <subscript>3</subscript> Fe-N═N═C(SiMe <subscript>3</subscript> ). This complex can be converted to the thermodynamically more favorable C -isocyanoamido isomer PhB(AdIm) <subscript>3</subscript> Fe-C═N═N(SiMe <subscript>3</subscript> ) by reaction with an additional equivalent of LiTMSD. While the iron(II) complexes are four-coordinate, the diazomethane is bound side-on in the iron(I) congener PhB(AdIm) <subscript>3</subscript> Fe( N , N '-κ <superscript>2</superscript> -N <subscript>2</subscript> C(H)Si(CH <subscript>3</subscript> ) <subscript>3</subscript> ). The latter complex adopts high spin ( S = 3/2) ground state and features an unusually weak C-H bond. Photolysis of the iron(II) complexes induces N═N bond cleavage, with the iron(II) cyanide PhB(AdIm) <subscript>3</subscript> Fe-C≡N and iron(IV) nitride PhB(AdIm) <subscript>3</subscript> Fe≡N complexes being the major products of the reaction. The same products are obtained when the iron(I) complex is photolyzed or treated with a fluoride source. The trimethylsilyldiazomethane-derived ligand disassembly reactions are contrasted with those observed for related tris(carbene)amine complexes.