124200-57-3Relevant academic research and scientific papers
π-Arene complexes. 6. Synthesis and characterization of η6-arene complexes of manganese with sulfur-containing ligands
Schindehutte, Minet,Van Rooyen, Petrus H.,Lotz, Simon
, p. 293 - 300 (2008/10/08)
The neutral complexes (η6-C6R6)Mn(CO)2(SPh) (R = H (1a), 3 H, 3 Me (1b), Me (1c)) have been prepared in high yields from the reaction of [(η6-C6R6)Mn(CO)3]PF6 with Me3NO and subsequent treatment of the reaction mixture with PhSH. Exchanging PhSH for PhSR′ (R′ = Ph, Me) in this reaction led to the formation of the cationic compounds [(η6-C6H3Me3)Mn(CO) 2(S(R′)Ph)]PF6 (R′ = Me (5), Ph (6)). Methylation of 1b with MeOSO2F again yielded 5. Protonation of 1a-c with HBF4 afforded the benzenethiol complexes [(η6-C6R6)Mn(CO) 2(S(H)Ph)]BF4 (R = H (4a), 3 H, 3 Me (4b), Me (4c)), which were characterized spectroscopically. Treatment of [(η6-C6R6)Mn(CO)2(THF)]PF 6 with thiophenol gave the cationic dimeric compounds [((η6-C6R6)Mn(CO)2) 2SPh]PF6 (R = H (2a), 3 H, 3 Me (2b), Me (2c)) in quantitative yields. The structures of 1a and 2b have been determined crystallographically. The neutral complex (η6-C6H6)Mn(CO)2SPh crystallizes in the monoclinic space group P21/n with a = 8.046 (3) A?, b = 14.735 (6) A?, c = 10.595 (5) A?, β = 98.11 (3)°, Z = 4, V = 1243 (1) A?3, R = 0.058, and Rw = 0.051. The structure adopted a staggered conformation of the two carbonyls and the sulfur ligand relative to the π-arene carbon atoms. The cationic compound [((η6-C6H3Me3)Mn(CO) 2)2SPh]PF6 crystallizes in the monoclinic space group P21/n with a = 8.340 (1) A?, b = 28.273 (3) A?, c = 13.350 (2) A?, β = 104.87 (1)°, Z = 4, V = 3043 (1) A?3, R = 0.059, and Rw = 0.047. The eclipsed conformations of the carbonyls and the sulfur ligands relative to the respective π-arene ring carbon atoms are slightly distorted.
