100993-30-4Relevant academic research and scientific papers
Cycloaddition and insertion reactions of N-sulfinylmethanesulfonamide and sulfur bis(methanesulfonylimide) with transition-metal-propargyl, -η1-allyl, and -cyclopropylmethyl complexes. Novel [3 + 3] cycloaddition products
Leung, Tak Wai,Christoph, Gary G.,Gallucci, Judith,Wojcicki, Andrew
, p. 846 - 853 (2008/10/08)
Reactions of the N-sulfinyl sulfonamides R′S(O)2NSO (R′ = Me, Ph) and sulfur bis(methanesulfonylimide) ([MeS(O)2N]2S) with transition-metal-propargyl, -η1-allyl, and -cyclopropylmethyl complexes have been investigated to complement previously reported studies of the corresponding reactions of SO2. Metalpropargyl complexes react at ambient temperatures with R′S(O)2NSO and [MeS(O)2N]2S to afford [3 + 2] cycloadducts MC=C(R)S(O)N[S(O)2R′]CH2 and MC=C(R)S[NS(O)2Me]N[S(O)2Me]CH2 (M = CpFe(CO)2, CpMo(CO)3, CpW(CO)3, CpCr(NO)2, Mn(CO)5; R = Me, Ph), respectively. Metal-η1-allyl complexes and MeS(O)2NSO at 25°C also furnish [3 + 2] cycloaddition products MCHCH2S(O)N[S-(O)2Me]CH2 (M = CpFe(CO)2, CpMo(CO)3, Mn(CO)5); however, η1-allyl complexes and [MeS(O)2N]2S yield novel [3 + 3] cycloadducts, MC(R)CH2N[S(O)2Me]SN[S(O)2Me]CH2 (M = CpFe(CO)2, CpMo(CO)3, Mn(CO)5; R = H, Me). The structure of CpFe(CO)2CHCH2N[S(O)2Me]SN[S(O) 2Me]CH2 was determined by X-ray diffraction analysis. The crystals are monoclinic of space group P21/n with a = 8.500 (1) A?, b = 19.656 (1) A?, c = 10.380 (1) A?, β = 98.25 (1)°, and Z = 4. Least-squares refinement (on F2) has resulted in a final value of R = 0.113 based on all the 5274 unique reflections. The six-membered heterocyclic ring adopts a chair conformation. The complex CpFe(CO)2CH2CHCH2CH2 reacts at room temperature with MeS(O)2NSO and [MeS(O)2N]2S to afford, in each case, products of insertion and cycloaddition. Thus, with the former, CpFe(CO)2{N[S(O)2Me]S(O)CH2CHCH 2CH2} (19%) and CpFe(CO)2CHCH2CH2S(O)-N[S(O) 2Me]CH2 (50%) are obtained, whereas with the latter, CpFe(CO)2{N[S(O)2Me]S-(CH2CHCH 2CH2NS(O)2Me} (52%) and CpFe(CO)2CHCH2CH2S[NS(O) 2Me]N[S(O)2Me]CH2 (28%) are isolated. There is no conversion of the insertion products into the corresponding cycloaddition products at room temperature in solution. Results of this study demonstrate that there are noticeable differences in the reaction of each of metal-η1-allyl and -cyclopropylmethyl complexes with SO2, MeS(O)2NSO, and [MeS(O)2N]2S. These differences are discussed.
