- N-(alkylsulfinyl)alkanesulfonamidato-N, N-[S-alkyl- N′-(alkylsulfonyl)sulfinimidoyl]-alkanesulfonamidato-N, and related complexes of dicarbonyl(η5-cyclopentadienyl)iron(II) derived by insertion of N-sulfinylsulfonamides and disulfonylsulfur diimides into iron-carbon σ bonds
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Reactions of the alkyl and aryl complexes η5-C5H5Fe(CO)2R with some electronic and structural analogues of SO2, viz., N-sulfinylamines, N-sulfinylsulfonamides, and disulfonylsulfur diimides, have been investigated. The N-sulfinylamines, C6H11NSO and C6H5NSO, do not react with η5-C5H5Fe(CO)2CH3at ambient temperatures; C6H11NSO reacts with η5-C5H5Fe(CO)2CH3 in the presence of BF3, but no stable product could be isolated and fully characterized. By contrast, under comparable conditions, more electrophilic N-sulfinylsulfonamides, R′S(O)2NSO, insert into the Fe-R σ bond of η5-C5H5Fe(CO)2R to yield N-bonded η5-C5H5Fe(CO) 2{N[S(O)R][S(O)2R′]} (1). Complexes 1 undergo ligand oxidation by m-ClC6H4C(O)OOH to the corresponding η5-C5H5Fe(CO)2{N[S(O) 2R][S(O)2R′]} (2) and linkage isomerization on heating in the solid or solution to η5-C5H5Fe(CO) 2{S(O)(R)[NS(O)2R′]} (3). Disulfonylsulfur diimides, [R′S(O)2N]2S, react at ambient temperatures with η5-C5H5Fe(CO)2R to yield N-bonded insertion products η5-C5H5Fe(CO)2{N[S-(O) 2R′][S(R)NS(O)2R′]} (4). The new complexes 1-4 have been characterized by a combination of IR and 1H and 13C NMR spectroscopy, in addition to chemical analysis. By the use of threo-η5-C5H5Fe(CO)2CHDCHDC 6H5 in conjunction with each of C6H5S(O)2NSO and [p-XC6H4S(O)2N]2S (X = H, Cl), it was demonstrated that the formation of the appropriate 1 and 4 proceeds with inversion of configuration at the α carbon of CHDCHDC6H5. A mechanism similar to that proposed for the SO2 insertion reaction of coordinatively saturated transition metal-alkyl carbonyl complexes appears likely.
- Severson, Roland G.,Leung, Tak Wai,Wojcicki, Andrew
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p. 915 - 923
(2008/10/08)
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