Reactions of lithium bis(μ-phenylphosphido)-bis(tricarbonyliron), (μ-PhPLi)2Fe2(CO)6, with organic halides. A novel anionic rearrangement of a chelating diphosphido ligand

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)

“…The 31 P NMR spectral data of 3 − 8 indicate that the 31 P chemical shifts for isomers e(R)e(H), e(R)a(H), and a(R)a(H) are in the range 90−96, 84−88, and 101−103 ppm, respectively, following the trend of a(R)a(H) > e(R)e(H) > e(R)a(H). Such 31 P NMR values are close to those of reported compounds, such as (μ-PhPH)(μ-η 5 -C 5 H 5 Fe(CO) 2 PhP)Fe 2 (CO) 6 (97.0 ppm) 13 and (μ-PhP−PPh-μ)[(μ-PhPH)Fe 2 (CO) 6 ] 2 (81.2 ppm) …”

“…In addition, the H atom of the neighboring CH group can also be coupled with the 31 P nucleus and the H atom of the PH group to give another two dd-type quartets at 3.83 and 4.15 ppm assigned to the H atom in the CH group of 3 e(R)e(H) and 3 e(R)a(H), respectively. It is worth noting that the coupling constants for these two isomers between 31 P and its directly linked H atom, namely, 1 J 1 H{ 31 P} are 350.2 and 360.2 Hz, which are similar to those reported for (μ-PhPH)(μ-η 5 -C 5 H 5 Fe(CO) 2 PhP)Fe 2 (CO) 6 and (μ-PhP−PPh-μ)[(μ-PhPH)Fe 2 (CO) 6 ] 2 …”

Aza-Diphosphido-Bridged Di-Iron Complexes Related to the [FeFe]-Hydrogenases

“…The complex [Fe2(CO)6(µ-{P(Ph)CH2}2N t Bu)] (1) was obtained from the reaction of t BuN(CH2Cl)2 with the dianion [Fe2(CO)6(µ-PPh)2] 2-(Scheme 2, path (a)). This la er dianion was prepared by the reaction of [Fe2(CO)6(µ-PHPh)2] with two equivalents of methyllithium [21,31,41]. In the presence of 1 equivalent of HBF4, Et2O, the protonation of 1 occurred at the nitrogen atom of the azadiphosphido bridge, which produced the cationic complex [Fe2(CO)6(µ-{P(Ph)CH2}2NH t Bu)](BF4) (3).…”

New chemical and stereochemical applications of organoiron complexes

“…A selected recent work on organosulfur-iron complexes includes reactions of lithium bis(η-phenylphosphido)-bis(tricarbonyliron) with organic halides [ 499 ], synthesis and reactivity of (η-σ-π-acetylide)(η-alkane- and η-arene-thiolate) bis(tricarbonyliron) complexes [ 500 ]; also synthesis of cis-trans -Fe(CyNC) 4 (SPh) 2 [ 501 ], chelation of iron (II)dithiocarbamates [ 502 ], thiolate, thioether, and thiol derivatives of iron (0) carbonyls [ 503 ], reaction of {CpFe(CO)MeCN) = C[SMe 2 ]} PF 6 with NaSMe [ 504 ], cyclodextrin sandwiched Fe 4 S 4 cluster [ 505 ], and iron-sulfur proteins containing Fe 2 S 2 clusters [ 506 , 507 ].…”