Amide-Directed Formation of Five-Coordinate Osmium Alkylidenes from Alkynes

作者：Casanova Noelia; Esteruelas Miguel A; Gulias Moises; Larramona Carmen; Mascarenas Jose L; Onate Enrique

来源：Organometallics, 2016, 35(2): 91-99.

DOI：10.1021/acs.organomet.5b00777

The amide-directed synthesis of five-coordinate osmium alkylidene derivatives from alkynes is reported. These types of complexes, which have been elusive until now because of the tendency of asmium to give hydride alkylidyne species, are prepared by reaction of the dihydride OsH2Cl2((PPr3)-Pr-i)(2) (1) with terminal alkynes containing a distal amide group. Complex 1 reacts with N-phenylhex-5-ynamide and N-phenylhepta-6-ynamide to give OsCl2{=C(CH3)(CH2)(n)NH(CO)Phl((PPr3)-Pr-i)(2) (n = 3 (2), 4 (3)). The relative position of carbonyl and NH groups in the organic substrates has no influence on the reaction. Thus, treatment of 1 with N-(pent-4-p-1-yObenzamide leads to OsCl2{=C(CH3)(CH2)(3)NHC(O)Ph}((PPr3)-Pr-i)(2) (4). The new compounds are intermediate species in the cleavage of the C-C triple bond of the alkynes. Under mild conditions, they undergo the rupture of the C-alpha-CH3 bond of the alkylidene, which comes from the alkyne triple bond, to afford six-coordinate hydride alkylidyne derivatives. In dichloromethane, complex 2 gives a 10:7 mixture of OsHCl2{ C(CH2)(3)C(O)NHPh}((PPr3)-Pr-i)(2) (5) and OsHCl2{ CCH(CH3)(CH2)(2)C(O)NHPh}((PPr3)-Pr-i)(2) (6). The first complex contains a linear separation between the alkylidyne C-alpha atom and the amide group, whereas the spacer is branched in the second complex. In contrast to the case for 2, complex 4 selectively affords OsHCl2{ C(CH2)(3)NHC(O)Ph}((PPr3)-Pr-i)(2) (7). In spite of their instability, these compounds give the alkylidene allene metathesis, being a useful entry to five-coordinate vinylidene complexes, including the dicarbon-disubstituted OsCl2(=C=CMe2)((PPr3)-Pr-i)(2) (8) and the monosubstituted OsCl2(=C=CHCy)((PPr3)-Pr-i)(2) (9).

• 出版日期2016-1-25