Intramolecular nucleophilic attack at iron in an anionic phosphido-bridged hexacarbonyldiiron [Fe2(CO)6] complex

Novel Reaction of Complex Salts [(μ-RE)(μ-CO)Fe2(CO)6][HNEt3] (E = S, Se) with Phosphaalkene t-Bu(Me3SiO)CPSiMe3. Synthesis and Spectroscopic and Crystallographic Characterization of Butterfly Fe2EP Clusters (μ-RE)[μ-t-Bu(Me3SiO)CHPH]Fe2(CO)6 (E = S, Se)

“…In 3 e(R)a(H), 6 e(R)a(H), 8 e(R)e(H), and 8 a(R)a(H), the Fe−P bond lengths of 2.203−2.231 Å and the Fe−P−Fe bond angles of 70.17−71.72° are about the same as those of the reported Fe 2 SP clusters mentioned above (2.194−2.233 Å, 70.6−72.6°). In addition, the P−C bond lengths in these four isomers (1.87−1.89 Å) are reasonable for a P−C single bond (1.79−1.99 Å) and very close to that (average 1.879 Å) in a similar compound, (μ- o -C 6 H 4 )(CH 2 PPh) 2 Fe 2 (CO) 6 …”

“…In addition, the P-C bond lengths in these four isomers (1.87-1.89 Å) are reasonable for a P-C single bond (1.79-1.99 Å) 20 and very close to that (average 1.879 Å) in a similar compound, (µ-o-C 6 H 4 )(CH 2 PPh) 2 Fe 2 (CO) 6 . 21 Mechanistic Considerations. According to the structures of products 3-8, the reaction between 1 and 2 would involve, at least, both addition of 1 toward the PdC double bond of 2 and replacement of SiMe 3 of 2 by a proton.…”

“…(1) Seyferth, D.;Womack, G. B.;Dewan, J. C. Organometallics 1985, 4, 398. (2) Seyferth, D.; Hoke, J. B.; Dewan, J. C. Organometallics 1987, 6, 895.…”

Formation of a Hexacarbonyl Diiron Complex Having a Naphthalene-1,8-bis(phenylphosphido) Bridge and the Electrochemical Behavior of Its Derivatives

“…Binuclear iron carbonyl complexes with chelating dithiolato ligands have been intensively investigated as hydrogenase models. In addition, many of their derivatives in which the terminal carbonyl ligands are replaced with phosphorus ligands have been prepared so far in order to explore the electronic perturbation of the redox properties. − ,,, On the other hand, although a variety of analogues having chelating bisphosphido ligands are also known, ,− only two reports have described a complex having a phosphine ligand at its terminal position. , …”

A Sterically Enforced Bent Form of an Edge-Sharing Dipalladium(II) Complex Attained by a Linked-Bisphosphido Bridge

“…On the other hand, to our knowledge, linked-bisphosphido groups have not been used as a bridging moiety in an edge-sharing square planar complex of d 8 transition metals. Of course some bimetallic complexes with linked-bisphosphido groups such as {RP−(linker)−PR} 2- (linker = (CH 2 ) n , 1,2-phenylene, or o -xylene) are known, − but they do not have edge-sharing square planar structures. In this paper, we describe the preparation and X-ray structure of linked-bisphosphido dipalladium(II) complexes with a formula [Pd 2 (μ-RPCH 2 CH 2 PR)(DPPE) 2 ]Cl 2 (R = Me and Ph), in which the linked-bisphosphido groups are employed as a ligand to enforce them sterically to adopt a bent structure.…”