Ru-Alkylidene Metathesis Catalysts Based on 1,3-Dimesityl-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidenes: Synthesis, Structure, and Activity

Kumar, PS; Wurst, K; Buchmeiser, MR

HERO ID

4936248

Reference Type

Journal Article

Year

2009

HERO ID 4936248
In Press No
Year 2009
Title Ru-Alkylidene Metathesis Catalysts Based on 1,3-Dimesityl-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidenes: Synthesis, Structure, and Activity
Authors Kumar, PS; Wurst, K; Buchmeiser, MR
Journal Organometallics
Volume 28
Issue 6
Page Numbers 1785-1790
Abstract Novel 1,3-dimesityl-4,5,6,7-tetrahydro-[1,3]-diazepin-2-ylidene-coordinated Ru-alkylidene complexes RuCl(2)(1,3-dimesityl-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene)(CH-2-(2-PrO)C(6)H(4)) (2) and Ru(CF(3)COO)(2) (1,3-dimesityl-4,5,6,7-tetrahydro-1,3-diazepin-2-ylidene)(=CH-2-(2-PrO)C(6)H(4)) (3) were synthesized from the first-generation Grubbs-Hoveyda catalyst, [RUCl(2)(PCy(3))(=CH-2-(2-PrO)C(6)H(4))] (1). The single-crystal X-ray structure of 3 was determined. Compound 2 showed excellent reactivity in ring-opening metathesis polymerization (ROMP) of cis-cycloocta-1,5-diene (COD), yielding polymers with a high trans-content of 80%. Compound 3 is also an active initiator for ROMP; however, a low trans-content of only 14% was found for poly-COD prepared by this initiator. Both 2 and 3 turned out to be good catalysts for cross-metathesis (CM), while both compounds showed only moderate activity in ring-closing rnetathesis (RCM). Finally, 3 is also a good polymerization catalyst for the regioselective cyclopolymerization of dipropargyl diethyl malonate (DEDPM), resulting in poly-DEDPM virtually solely based on five-membered repeat units.
Doi 10.1021/om801213t
Wosid WOS:000264273700024
Is Certified Translation No
Dupe Override No
Is Public Yes