摘要
Reaction of [PPN][Fe(NO) 2 (SePh) 2 ] (1) with dimeric [Ni(μ-SCH 2 CH 2 SCH 2 CH 2 S)] 2 in the presence of additional NO 2 - produced the neutral heterobimetallic [(ON)Ni{μ-SCH 2 CH 2 ) 2 S}Fe(NO) 2 ] complex (2). The X-ray crystal structures of 1 and 2 show distorted tetrahedral iron dinitrosyl groups, assigned according to the Feltham-Enemark notation as {Fe(NO) 2 } 9 . The Fe-NO bonds are off linearity by an average of ≃ 10°for compounds 1 and 2, while a more linear Ni-NO coordination with a Ni-NO distance of 1.644(2) Å was found in 2. The ν(NO) value of complex 2 is consistent with an assignment for {Ni(NO)} 9 of Ni 0 (NO) + as is known for analogous phosphine derivatives, P 3 Ni 0 (NO) + . EPR signals of g values = 2.02-2.03 confirmed the existence of the odd electron in the chalcogenated {Fe(NO) 2 } 9 compounds. Two {Fe(NO) 2 } 10 complexes coordinated by the nickel(II) dithiolate, (bismercaptoethanediazacyclooctane)nickel(II), (Ni-1), (Ni-1)Fe(CO)(NO) 2 and (Ni-1)Fe(NO) 2 , were prepared for comparison to the Ni 0 (NO) + derivative and other monomeric and homodimetallic derivatives of the Fe(NO) 2 fragment. While the oxidation level of Fe(NO) 2 is the primary determinant of ν(NO) values, they are also highly sensitive to ancillary ligands and, thereby, the distal metal influence through the bridging thiolate donor.