Syntheses of Molybdenum Oxo Alkylidene Complexes through Addition of Water to an Alkylidyne Complex
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资源简介：
Addition of one equiv
of water to Mo(CAr)[OCMe(CF3)2]3(1,2-dimethoxyethane)
(2, Ar = o-(OMe)C6H4) in the presence of PPhMe2 leads to formation of Mo(O)(CHAr)[OCMe(CF3)2]2(PPhMe2) (3(PPhMe2)) in 34% yield. Addition of
one
equiv of water alone to 2 produces the dimeric alkylidyne
hydroxide complex, {Mo(CAr)[OCMe(CF3)2]2(μ-OH)}2(dme) (4(dme)) in which
each bridging hydroxide proton points toward an oxygen atom in an
arylmethoxy group. Addition of PMe3 to 4(dme) gives the alkylidene oxo complex, (3(PMe3)), an analogue of 3(PPhMe2) (95% conversion, 66% isolated).
Treatment of 3(PMe3) with two equiv of HCl gave Mo(O)(CHAr)Cl2(PMe3) (5), which upon addition of LiO-2,6-(2,4,6-i-Pr3C6H2)2C6H3 (LiOHIPT) gave Mo(O)(CHAr)(OHIPT)Cl(PMe3) (6). Compound 6 in the presence
of B(C6F5)3 will initiate the ring-opening
metathesis polymerization of cyclooctene, 5,6-dicarbomethoxynorbornadiene
(DCMNBD), and rac-5,6-dicarbomethoxynorbornene (DCMNBE),
and the homocoupling of 1-decene to 9-octadecene. The poly(DCMNBD)
has a cis,syndiotactic structure, whereas poly(DCMNBE)
has a cis,syndiotactic,alt structure. X-ray structures
were obtained for 3(PPhMe2), 4(dme), and 6.
创建时间：
2018-02-16
