Coordinated nitrosyl as a source of oxygen: reactivity of the dinitrosyliron moiety in the presence of the bidentate phosphane 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(diphenylphosphino)ethene (dppen)

Abstract

The nitrosyl dimer [Fe(NO)2Cl]2 (1) in the presence of l,2-bis(diphenylphosphino)ethane (dppe) or tra/u-l,2-bis(diphenylphosphino)ethene (tdppen) yields the binuclear complex [Fe(NO)2Cl]2(^-dppe) (2) or [Fe(NO)2Cl]2fii-tdppen) (6). In the presence of excess diphosphine dppe, tdppen, or cis-1,2-bis(diphenylphosphino)ethene (cdppen), the Fe(NO)2X moiety undergoes (i) halogen displacement to yield Fe(NO)2(PP) complexes of |Fe(NO)2)10 configuration and (ii) unexpectedly, NO substitution, which results in Fe(NO)Cl2(OPP) species of |Fe(NO)|9 configuration, where the diphosphine has been monooxygenated by NO.

The synthesis and structural characterization of linear and macrocyclic bis(dinitrosyliron) complexes supported by bis(phosphine) bridging ligands

“…The iron-iron distances in both the linear (4,~5.2 Å; 5,~7.6 Å) and macrocyclic (8,~4.4 Å; 9,~7.0 Å) compounds are all significantly longer than the related distances found in other structurally characterized bis(dinitrosyliron) species described as possessing a metalmetal bond (23). The crystallographically determined structures of the linear species, 4 and 5, can be compared with that of [Fe(NO) 2 Cl] 2 (µ-DPPE) (DPPE = 1,2-bis(diphenylphosphino)ethane), where DPPE stands as a single bridge joining the two metal centers (17).…”

“…Moreover, Hong and co-workers have shown that dinuclear Group 10 complexes of the type cyclo[M(κ 2 -DPPM)] 2 (µ-DPPA) 2 (DPPA = bis(diphenylphosphino)acetylene) exhibit interesting photoluminescent behavior (16). Despite the well-established history of dinuclear bis(phosphine) complexes in the field of inorganic chemistry, bis(dinitrosyliron) derivatives of this class are still rare, and their reactivity properties remain essentially unexplored (17).…”

The Preparation, Structural Characteristics, and Physical Chemical Properties of Metal-Nitrosyl Complexes

“…Despite the well-established history of dinuclear bis (phosphine) complexes in the field of inorganic chemistry, bis(dinitrosyliron) derivatives of this class are still rare and their properties remain essentially unexplored with the exception of a few select structures [35, 36]. Depending on the reaction conditions employed, either linear diiron constructs connected by one bis(phosphine) linker, (NO) 2 FeP~PFe(NO) 2 , or macrocyclic species spanned by two bridging ligands, [(NO) 2 Fe] 2 (P~P) 2 , can be obtained [35].…”

“…Depending on the reaction conditions employed, either linear diiron constructs connected by one bis(phosphine) linker, (NO) 2 FeP~PFe(NO) 2 , or macrocyclic species spanned by two bridging ligands, [(NO) 2 Fe] 2 (P~P) 2 , can be obtained [35]. …”

“…The iron–iron distances in both the linear ( 7 , ~5.2 Å; 8 , ~7.6 Å) and macrocyclic ( 11 , ~4.4 Å; 12 , ~7.0 Å) compounds are all significantly longer than the related distances found in other structurally characterized species that are described as possessing a metal–metal bond. The crystallographically determined structures of the linear species, 7 and 8 , can be compared with that of [Fe(NO) 2 Cl] 2 (μ-DPPE) (DPPE = 1,2-bis(diphenylphosphino)ethane), where DPPE stands as a single bridge joining the two metal centers [35]. …”