Alkyne metatheses in transition metal coordination spheres: Convenient tungsten- and molybdenum-catalyzed syntheses of novel metallamacrocycles

abstract

• AbstractReactions of (CO)5Re(Br), (5C5H5)Ru(Cl)(PPh3)2, and [Pt(Cl)(C6F5)(S(CH2CH2)2)]2 with the alkynecontaining phosphine Ph2P(CH2)6CCCH3 give the bis(phosphine) complexes fac(CO)3Re(Br)(Ph2P(CH2)6CCCH3)2 (5), (5C5H5)Ru(Cl)(Ph2P(CH2)6CCCH3)2 (6), and trans(Cl)(C6F5)Pt(Ph2P(CH2)6CCCH3)2 (7). Alkyne metatheses with the catalyst (tBuO)3W(CtBu) (1015mol%, chlorobenzene, 80C) give the seventeenmembered metallamacrocycles fac(CO)3Re(Br)(Ph2P(CH2)6CC(CH2)6PPh2) (8), (5C5H5)Ru(Cl)(Ph2P(CH2)6CC(CH2)6PPh2) (9), and trans(Cl)(C6F5)Pt(PPh2(CH2)6CC(CH2)6PPh2) (10). 31PNMR analyses show 9075% conversions to 810 (5947% isolated after chromatography). The identity of 8 was confirmed by a crystal structure, and 10 was hydrogenated over Pd/C to fac(CO)3Re(Br)(Ph2P(CH2)6CC(CH2)6PPh2) (12, 87%), which was crystallographically characterized earlier. A catalyst derived from Mo(CO)6/4chlorophenol effects a slower conversion of 7 to 10 at 140C. In the case of 5, a mer,trans isomer of 8 is isolated (11, 44%), as established by NMR and IR data. In 1012, the diphosphines span trans positions. These results, together with previous examples involving group VIII metallocenes, establish the wide viability of the title reaction.

authors

• Gladysz, John

published proceedings

• ADVANCED SYNTHESIS & CATALYSIS

author list (cited authors)

• Bauer, E. B., Hampel, F., & Gladysz, J. A.

citation count

• 24

complete list of authors

• Bauer, EB||Hampel, F||Gladysz, JA

publication date

• June 2004

publisher

• Wiley  Publisher

published in

• Advanced Synthesis and Catalysis  Journal

keywords

• Alkylidyne Complexes
• Alkynes
• Macrocycles
• Metathesis
• Molybdenum
• Rhenium
• Tungsten

Digital Object Identifier (DOI)

• 10.1002/adsc.200404026

start page

• 812

end page

• 822

volume

• 346

issue

• 7

URL

• https://doi.org/10.1002/adsc.200404026