Calcium formamidinate derivatives by hydride insertion of carbodiimides

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 48; no. 13; pp. 4248 - 4254
• Main Authors: Dyall, Joshua, Hill, Michael S, Mahon, Mary F, Teh, Luke, Wilson, Andrew S S
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 26.03.2019
• Subjects: Calcium; Carbodiimides; Chemical reduction; Constitution; Crystallography; Derivatives; Dimers; Hydrides; NMR; Nuclear magnetic resonance; Reagents
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c8dt05107k

The carbodiimides, Ar/RN[double bond, length as m-dash]C[double bond, length as m-dash]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-Pr2C6H3}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.