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Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes.

Publication ,  Journal Article
Lichtscheidl, AG; Ng, VWL; Müller, P; Takase, MK; Schrock, RR; Malcolmson, SJ; Meek, SJ; Li, B; Kiesewetter, ET; Hoveyda, AH
Published in: Organometallics
June 2012

Seven bipyridine adducts of molybdenum imido alkylidene bispyrrolide complexes of the type Mo(NR)(CHCMe(2)R')(Pyr)(2)(bipy) (1a-1g; R = 2,6-i-Pr(2)C(6)H(3) (Ar), adamantyl (Ad), 2,6-Me(2)C(6)H(3) (Ar'), 2-i-PrC(6)H(4) (Ar(iPr)), 2-ClC(6)H(4) (Ar(Cl)), 2-t-BuC(6)H(4) (Ar(t) (Bu)), and 2-MesitylC(6)H(4) (Ar(M)), respectively; R' = Me, Ph) have been prepared using three different methods. Up to three isomers of the adducts are observed that are proposed to be the trans and two possible cis pyrrolide isomers of syn alkylidenes. Sonication of a mixture containing 1a-1g, HMTOH (2,6-dimesitylphenol), and ZnCl(2)(dioxane) led to the formation of MAP species of the type Mo(NR)(CHCMe(2)R')(Pyr)(OHMT) (3a-3g). DCMNBD (2,3-dicarbomethoxynorbornadiene) is polymerized employing 3a-3g as initiators to yield >98% cis,syndiotactic poly(DCMNBD). Attempts to prepare bipy adducts of bisdimethylpyrrolide complexes led to formation of imido alkylidyne complexes of the type Mo(NR)(CCMe(2)R')(Me(2)Pyr)(bipy) (Me(2)Pyr = 2,5-dimethylpyrrolide; 4a - 4g) through a ligand-induced migration of an alkylidene α proton to a dimethylpyrrolide ligand. X-ray structures of Mo(NAr)(CHCMe(2)Ph)(Pyr)(2)(bipy) (1a), Mo(NAr(iPr))(CHCMe(2)Ph)(Pyr)(OHMT) (3d), Mo(NAr)(CCMe(2)Ph)(Me(2)Pyr)(bipy) (4a), and Mo(NAr(T))(CCMe(3))(Me(2)Pyr)(bipy) (Ar(T) = 2-(2,4,6-i-Pr(3)C(6)H(2))C(6)H(4); 4g) showed structures with the normal bond lengths and angles.

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Published In

Organometallics

DOI

EISSN

1520-6041

ISSN

0276-7333

Publication Date

June 2012

Volume

31

Issue

12

Start / End Page

4558 / 4564

Related Subject Headings

  • Organic Chemistry
  • 3406 Physical chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0305 Organic Chemistry
  • 0302 Inorganic Chemistry
 

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Lichtscheidl, A. G., Ng, V. W. L., Müller, P., Takase, M. K., Schrock, R. R., Malcolmson, S. J., … Hoveyda, A. H. (2012). Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes. Organometallics, 31(12), 4558–4564. https://doi.org/10.1021/om300353e
Lichtscheidl, Alejandro G., Victor W. L. Ng, Peter Müller, Michael K. Takase, Richard R. Schrock, Steven J. Malcolmson, Simon J. Meek, Bo Li, Elizabeth T. Kiesewetter, and Amir H. Hoveyda. “Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes.Organometallics 31, no. 12 (June 2012): 4558–64. https://doi.org/10.1021/om300353e.
Lichtscheidl AG, Ng VWL, Müller P, Takase MK, Schrock RR, Malcolmson SJ, et al. Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes. Organometallics. 2012 Jun;31(12):4558–64.
Lichtscheidl, Alejandro G., et al. “Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes.Organometallics, vol. 31, no. 12, June 2012, pp. 4558–64. Epmc, doi:10.1021/om300353e.
Lichtscheidl AG, Ng VWL, Müller P, Takase MK, Schrock RR, Malcolmson SJ, Meek SJ, Li B, Kiesewetter ET, Hoveyda AH. Bipyridine Adducts of Molybdenum Imido Alkylidene and Imido Alkylidyne Complexes. Organometallics. 2012 Jun;31(12):4558–4564.
Journal cover image

Published In

Organometallics

DOI

EISSN

1520-6041

ISSN

0276-7333

Publication Date

June 2012

Volume

31

Issue

12

Start / End Page

4558 / 4564

Related Subject Headings

  • Organic Chemistry
  • 3406 Physical chemistry
  • 3402 Inorganic chemistry
  • 0399 Other Chemical Sciences
  • 0305 Organic Chemistry
  • 0302 Inorganic Chemistry