99475-78-2Relevant academic research and scientific papers
Insertion reactions of N-sulfinyl sulfonamides and sulfur bis(sulfonylimide)s into transition-metal-carbon σ bonds
Leung, Tak Wai,Christoph, Gary G.,Gallucci, Judith,Wojcicki, Andrew
, p. 366 - 374 (2008/10/08)
Insertion reactions have been investigated of the N-sulfinyl sulfonamides R′S(O)2NSO (R′ = Me, p-ClC6H4) and the sulfur bis(sulfonylimide) [MeS(O)2N]2S into the metal-carbon σ bonds of CpFe(CO)(L)Me (L = PPh3, P(OPh)3), CpM(CO)2(L)Me (M = Mo, W; L = PMe2Ph, PPh3), CpM(CO)3R (M = Mo, W; R = Me, CH2C6H4Cl-p), Mn(CO)4(L)Me (L = CO, PPh3), and CpCr(NO)2Me. The complexes CpFe(CO)(L)Me and CpM(CO)2(L)Me react with R′S(O)2NSO initially to yield insertion products containing the N-bonded N[S(O)2R′]S(O)Me ligand; these complexes rearrange upon warming or column chromatography to isolable S-bonded S[NS(O)2R′](O)Me linkage isomers. Reaction between CpCr(NO)2Me and MeS(O)2NSO affords CpCr(NO)2{N[S(O)2Me]S(O)Me}, which could not be converted to its S-bonded isomer. The complexes CpM(CO)3R react with MeS(O)2NSO to give the N- and O-bonded species CpM(CO)3{N[S(O)2Me]S(O)R} and CpM(CO)3{OS[NS(O)2Me]R}, respectively, in solution at -25°C; these compounds decompose upon warming to intractable materials. Treatment of Mn(CO)5Me with MeS(O)2NSO affords Mn(CO)5{N[S(O)2Me]S(O)Me} at -25°C in solution. Insertion reactions of [MeS(O)2N]2S with the aforementioned metal-Me complexes proceed to the appropriate compounds containing the N[S(O)2Me]S(Me)NS(O)2Me ligand. These complexes were generally isolated as end products; however, with Mn(CO)4(L)Me, further reaction occurred to yield isolable (CO)3(L)Mn{N[S(O)2Me]S(Me)NS(O)2Me} containing a bidentate insertion ligand. Reactions with HPF6·OEt2 and Et3OPF6 of CpFe(CO)2{N[S(O)2Me]S(O)Me} (1), CpFe(CO)2{N[S(O)2Me]S(Me)NS(O)2Me} (2), and CpFe(CO)2{S[NS(O)2Me](O)Me} (3) lead to protonation at nitrogen in 1, 2 (uncoordinated N), and 3 and alkylation at the sulfinyl oxygen in 1 and 3. The structure of CpFe(CO)2{S[NS(O)2Me](O)CH 2Ph}·1/2CH2Cl2 was determined by a single-crystal X-ray diffraction analysis. The crystals are triclinic of space group P1 with a = 8.517 (7) A?, b = 10.624 (5) A?, c = 12.092 (9) A?, α = 109.58 (5)°, β = 90.05 (6)°, γ = 108.06 (5)°, and Z = 2. The structure was solved and refined to R = 0.040 and Rw = 0.040 by using 2178 independent reflections. The Fe-S bond distance is 2.212 (1) A?, suggesting some double-bond character in this linkage.
