The reactivity of TMSN 3 with ruthenium cyclopropenyl complexes containing different ligands and different substituent at Cγ

Abstract

Ruthenium vinylidene complexes 2a– 2c containing indenyl and bidentate dppe ligands can be obtained in efficient yields. Treatment of the cationic ruthenium vinylidene complexes with n-Bu 4NOH in acetone yields the neutral cyclopropenyl products ( η 5-C 9H 7)(dppe)Ru–C C(Ph)CHR ( 3) ( 3a, R = Ph; 3b, R = CN; 3c, R = p-C 6H 4–CN) via the deprotonation reaction. Reaction of complexes 3a and 3c with Me 3SiN 3 (TMSN 3) the N-coordinated complexes 4a and 4c can be obtained as stable products. Complex 3b containing CN group at Cγ in the cyclopropenyl ring reacts with TMSN 3 yielded the tetrazolate complex 5b. Similar cyclopropenyl products containing indenyl and two triphenylphosphine ligands 3′ can also be synthesized. Reaction of complex 3b′ with TMSN 3 also yielded the tetrazolate complex as the major product. And the minor products are [Ru]–N 3 and organic compound 6b. Reaction of 3a′ and 3c′ with TMSN 3 yielded [Ru]–N 3. The corresponding organic products can also be obtained via the N 3 − attacking the metal center in the N-coordinated complexes 4a′ and 4c′.