Tethered alkylidenes from organoazides for cyclic polymer synthesis

A catalyst having a structure represented by formula (I), or dimers thereof:

• wherein
• M is a transition metal;
• L is absent or selected from the group of NH3, N(R5)3, Ar1, C1-6hydroxyalkyl, N≡C—R5, N═C(R5)2, OR5, O(R5)2, P(R5)3, P(OR5)3, PR5(OR5)2, PR52(OR5), R5(CO)N(R5)2, R5(CO)NHR5, R5CHO, R5COR5, R5COOR5, SR5, and S(R5)2;
• R1 is selected from H, N═N—Ra, C1-C20alkyl, C3-8cycloalkyl, C1-C20haloalkyl, Si—(R5)3, and Ar1, and Ra is selected from H, C1-C20alkyl, C3-8cycloalkyl, and Ar1;
• R2 is selected from H, Ar1, C1-C20alkyl, C5-C8cycloalkyl, halo, C1-20haloalkyl, NH2, N(C1-C20alkyl)2, NH(C1-C20alkyl), NHAr1, N(Ar1)2, OH, OAr1, and O(C1-C20alkyl);
• each R3 is independently selected from H, Ar1, C1-C20alkyl, C5-C8cycloalkyl, halo, C1-C20haloalkyl, COOH, COOC1-C20alkyl, NH2, N(C1-C20alkyl)2, NH(C1-C20alkyl), NHAr1, N(Ar1)(C1-20alkyl), N(Ar1)2, SH, OAr1, O(C1-C20alkyl), and OH, or R3 together with an adjacent R4 and the carbon atoms to which they are attached form a five- to eight-membered cyclic group;
• each m is independently 0, 1, 2, or 3;
• each R4 is independently selected from Ar1, C1-C20alkyl, C5-C8cycloalkyl, C1-C20haloalkyl, COOH, COOC1-C20alkyl, NH2, N(C1-C20alkyl)2, NH(C1-C20alkyl), NHAr1, N(Ar1)(C1-20alkyl), N(Ar1)2, SH, halo, and OH, or two adjacent R4, together with the carbon atoms to which they are attached, can form a five- to eight-membered cyclic group;
• each R5 is independently selected from H, C1-C20alkyl, C5-C8cycloalkyl, Ar1, or two R5, together with the atoms to which they are attached, form a five- to eight-membered heterocycle comprising from 1 to 3 ring heteroatoms selected from O, N, and S;
• and
• each Ar1 is independently selected from C0-C3alkylene-C6-20 aryl, or a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S.