Insertion reactions of beta-diketiminate-stabilised calcium amides with 1,3-dialkylcarbodiimides |
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Authors: | Barrett Anthony G M Crimmin Mark R Hill Michael S Hitchcock Peter B Procopiou Panayiotis A |
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Affiliation: | Department of Chemistry, Imperial College London, Exhibition Road, South Kensington, London, UKSW7 2AZ. |
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Abstract: | A series of heteroleptic beta-diketiminate-stabilised calcium amides of the form [{ArNC(Me)CHC(Me)NAr}Ca{NR(1)R(2)}(THF)] (Ar = 2,6-diisopropylphenyl; R(1) = H, R(2) = Ar; R(1) = H, R(2) = CH(2)CH(2)OMe; R(1) = R(2) = Ph) react with 1,3-dialkylcarbodiimides, R(3)N[double bond, length as m-dash]C[double bond, length as m-dash]NR(3) (R(3) = Cy, (i)Pr), to yield the corresponding insertion products [{ArNC(Me)CHC(Me)NAr}Ca{(R(3)N)(2)CNR(1)R(2)}(THF)] at room temperature in hydrocarbon solutions. These latter compounds contain both beta-diketiminate and guanidinate ligands bound to calcium. Solid-state data are consistent with the guanidinate ligands adopting a number of binding modes including kappa(2) through kappa(3) coordination, with varying degrees of delocalisation of the non-bound guanidinate nitrogen lone-pair across the pi-framework of the ligand. DFT computational studies have been conducted to address these variations in coordination behaviour. |
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