A binuclear guanidinate yttrium carbyne complex: unique reactivity toward unsaturated C-N, C-O and C-S bonds

A guanidinato-stabilized binuclear yttrium carbyne complex [(PhCH2)(2)NC((NC6H3Pr2)-Pr-i-2,6)(2)](2)Y-2(mu(2)-Me)(AlMe3)(2)(mu(4)-CH) (1) was synthesized via C-H bond activation and its versatile reactivities were investigated. Complex 1 underwent sigma-bond metathesis with PhSSPh and nucleophilic addition with PhCN to form the corresponding yttrium thiolate complex 3 and aza-allyl complex 4 respectively. Additionally, the rare yttrium carbide complex 5 was also prepared by treatment of complex 1 with S-8. Interestingly, in the reaction with PhNCS, the C=S double bond was cleaved, followed by C-H bond activation to give the yttrium sulfide complex 7 with a ketenimine dianion ligand. Unexpectedly, the reaction of complex 1 with CO (1 atm) resulted in deoxygenative coupling of CO, to afford mono- or dioxo-yttrium complexes at different temperatures. The mechanism of the possible formation processes of complexes 3 and 9 was elucidated by DFT calculations.