摘要
Reaction of Fe(CO) 2 (NO) 2 and [(ON)Fe(S,S-C 6 H 3 R) 2 ] - (R = H (1), CH 3 (1-Me))/[(ON)Fe(SO 2 ,S-C 6 H 4 )(S,S-C 6 H 4 )] - (4) in THF afforded the diiron thiolate/sulfinate nitrosyl complexes [(ON)Fe(S,S-C 6 H 3 R) 2 Fe(NO) 2 ] - (R = H (2), CH 3 (2-Me)) and [(ON)Fe(S,SO 2 -C 6 H 4 )(S,S-C 6 H 4 )Fe(NO) 2 ] - (3), respectively. The average N-O bond lengths ([Fe-(NO )2 ] unit) of 1.167(3) and 1.162(4) Å in complexes 2 and 3 are consistent with the average N-O bond length of 1.165 Å observed in the other structurally characterized dinitrosyl iron complexes with an {Fe(NO) 2 } 9 core. The lower v( 15 NO) value (1682 cm -1 (KBr)) of the [( 15 NO)FeS 4 ] fragment of [( 15 NO)Fe(S,S-C 6 H 3 CH 3 ) 2 Fe(NO) 2 ] - (2-Me- 15 N), compared to that of [( 15 NO)Fe(S, S-C 6 H 3 CH 3 ) 2 ] - (1-Me- 15 N) (1727 cm -1 (KBr)), implicates the electron transfer from {Fe(NO) 2 } 10 Fe(CO) 2 (NO) 2 to complex 1-Me/1 may occur in the process of formation of complex 2-Me/2. Then, the electronic structures of the [(NO)FeS 4 ] and [S 2 Fe(NO) 2 ] cores of complexes 2,2-Me, and 3 were best assigned according to the Feltham-Enemark notation as the {Fe(NO)} 7 -{Fe(NO) 2 } 9 coupling (antiferromagnetic interaction with a J value of -182 cm -1 for complex 2) to account for the absence of paramagnetism (SQUID) and the EPR signal. On the basis of Fe-N(O) and N-O bond distances, the dinitrosyliron {L 2 Fe(NO) 2 } derivatives having an Fe-N(O) distance of ∼1.670 Å and a N-0 distance of ∼1.165 Å are best assigned as {Fe(NO) 2 } 9 electronic structures, whereas the Fe-N(O) distance of ∼1.650 Å and N-O distance of ∼1.190 Å probably imply an {Fe(NO) 2 } 10 electronic structure. © 2005 American Chemical Society.