Alkyne Metatheses in Transition Metal Coordination Spheres: Convenient Tungsten- and Molybdenum-Catalyzed Syntheses of Novel Metallamacrocycles
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Reactions of (CO)5Re(Br), (5-C5H 5) Ru(Cl)(PPh3)2, and [Pt(-Cl)(C 6F5)(S(CH2CH2-)2)] 2 with the alkyne-containing phosphine Ph2P(CH 2)6 CCCH3 give the bis(phosphine) complexes fac-(CO)3Re(Br)(Ph2P(CH2) 6CCCH3)2 (5), (5-C 5H5) Ru(Cl)(Ph2P(CH2) 6CCCH3)2 (6), and trans-(Cl) (C 6F5)Pt(Ph2P(CH2)6C CCH3)2 (7). Alkyne metatheses with the catalyst (t-BuO)3W(C-t-Bu) (10-15 mol %, chlorobenzene, 80C) give the seventeen-membered metallamacrocycles fac-(CO)3Re(Br)(Ph 2P(CH2)6CC(CH2) 6PPh2) (8), 5-C5H 5)Ru(Cl)(Ph2P(CH2)6CC(CH 2)6PPh2) (9), and trans-(Cl)(C 6F5)Pt(PPh2(CH2)6C C(CH2)6PPh2) (10). 31P NMR analyses show 90-75% conversions to 8-10 (59-47% 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)6/4-chlorophenol 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 10-12, the diphosphines span trans positions. These results, together with previous examples involving group VIII metallocenes, establish the wide viability of the title reaction.
Advanced Synthesis & Catalysis
author list (cited authors)
Bauer, E. B., Hampel, F., & Gladysz, J. A.
complete list of authors
Bauer, Eike B||Hampel, Frank||Gladysz, JA