Calcium formamidinate derivatives by hydride insertion of carbodiimides. Issue 13 (8th March 2019)

• Record Type: Journal Article
• Authors: Dyall, Joshua; Hill, Michael S.; Mahon, Mary F.; Teh, Luke; Wilson, Andrew S. S.
• Is Part Of: Dalton transactions. Volume 48:Issue 13(2019)
• Page Start: 4248
• Page End: 4254
• Publication Date: 2019-03-08
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c8dt05107k
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Insertion reactions of N, N ′-dialkyl and N, N ′-diaryl carbodiimides with a dimeric calcium hydride provide formamidinate derivatives whose structures on the steric demands of the carbodiimide reagent. Abstract : The carbodiimides, Ar/RNCNAr/R, (Ar = 2, 6-di-isopropylphenyl (Dipp), 4-methylphenyl; R = tert -butyl, cyclohexyl, iso-propyl), react with the polar Ca–H bonds of the dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CN-2, 6-i-Pr2 C6 H3 }2 ), to provide a series of heteroleptic calcium formamidinate derivatives. While reactions with carbodiimides bearing more sterically demanding substituents (Dipp, t -Bu, Cy) are straightforward, and provide four-coordinate compounds, less bulky iso-propyl or 4-methylphenyl substitution results in the sequestration of a further equivalent of the carbodiimide and the isolation of a heteroleptic hydride-bridged dinuclear species. This latter observation is suggested to be a reflection of the robust dimeric constitution of the calcium hydride reagent and the reduced steric demands of the di- para -tolyl carbodiimide reagent.