title: Synthesis and Evaluation of Molybdenum and Tungsten Monoaryloxide Halide Alkylidene Complexes for Z-Selective Cross-Metathesis of Cyclooctene and Z-1,2-Dichloroethylene.
abstract: Molybdenum complexes with the general formula Mo(NR)(CHR')(OR″)(Cl)(MeCN) (R = t-Bu or 1-adamantyl; OR″ = a 2,6-terphenoxide) recently have been found to be highly active catalysts for cross-metathesis reactions between Z-internal olefins and Z-1,2-dichloroethylene or Z-(CF3)CH═CH(CF3). In this paper we report methods of synthesizing new potential catalysts with the general formula M(NR)(CHR')(OR″)(Cl)(L) in which M = Mo or W, NR = N-2,6-diisopropylphenyl or NC6F5, and L is a phosphine, a pyridine, or a nitrile. We also test and compare all catalysts in the cross-metathesis of Z-1,2-dichloroethylene and cyclooctene. Our investigations indicate that tungsten complexes are inactive in the test reaction either because the donor is bound too strongly or because acetonitrile inserts into a W═C bond. The acetonitrile or pivalonitrile Mo(NR)(CHR')(OR″)(Cl)(L) complexes are found to be especially reactive because the 14e Mo(NR)(CHR')(OR″)Cl core is accessible through dissociation of the nitrile to a significant extent. Pivalonitrile can be removed (>95%) from Mo(NAr)(CHCMe2Ph)(OHMT)(Cl)(t-BuCN) (Ar = 2,6-diisopropylphenyl; OHMT = 2,6-dimesitylphenoxide) to give 14e Mo(NAr)(CHCMe2Ph)(OHMT)Cl in solution as a mixture of syn and anti (60:40 at 0.015 M) nitrile-free isomers, but these 14e complexes have not yet been isolated in pure form. The syn isomer of Mo(NAr)(CHCMe2Ph)(OHMT)Cl binds pivalonitrile most strongly. Other Mo(NR)(CHR')(OR″)(Cl)(L) complexes can be activated through addition of B(C6F5)3. High stereoselectivities (>98% Z,Z) of ClCH═CH(CH2)6CH═CHCl are not restricted to tert-butylimido or adamantylimido complexes; 96.2% Z selectivity is observed with boron-activated Mo(NC6F5)(CHR')(OHIPT)(Cl)(PPhMe2). So far no Mo═CHCl complexes, which are required intermediates in the test reaction, have been observed in NMR studies at room temperature.
authors.affiliation: Department of Chemistry 6-331, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Jonathan K
authors.initials: JK
authors.lastname: Lam
authors.affiliation: Department of Chemistry 6-331, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Congqing
authors.initials: C
authors.lastname: Zhu
authors.affiliation: Department of Chemistry 6-331, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Konstantin V
authors.initials: KV
authors.lastname: Bukhryakov
authors.affiliation: Department of Chemistry 6-331, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Peter
authors.initials: P
authors.lastname: Müller
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College , Chestnut Hill, Massachusetts 02467, United States.
authors.forename: Amir
authors.initials: A
authors.lastname: Hoveyda
authors.affiliation: Department of Chemistry 6-331, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Richard R
authors.initials: RR
authors.lastname: Schrock
mesh_terms: D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D034242:Cyclooctanes / Q000737:chemistry; D004000:Dichloroethylenes / Q000737:chemistry; D006219:Halogens / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D008982:Molybdenum / Q000737:chemistry; D010087:Oxides / Q000737:chemistry; D013237:Stereoisomerism; D014414:Tungsten / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D034242:Cyclooctanes; D004000:Dichloroethylenes; D006219:Halogens; D010087:Oxides; D008982:Molybdenum; D014414:Tungsten; C035384:1,2-dichloroethylene