P−C Bond Cleavage of Phosphorus-Bridged [1]Ferrocenophane Coordinated to the [Cp(CO)₂Fe]⁺ Fragment

Abstract

An iron complex with (1,1‘-ferrocenediyl)phenylphosphine (FCPP) as a ligand, [Cp(CO)2Fe(FCPP)]+, was prepared, and its PF6 - salt was subjected to X-ray crystal structure analysis. Photoirradiation of the PF6 - salt resulted in Cp ring migration from a P to an Fe atom. Addition of H2O or (n-Bu)4NF to the reaction mixture gave an isolable complex, formulated as [Cp(CO)Fe(C5H4FeC5H4PFPh)]. The structure for one of the racemic isomers was determined with X-ray analysis. This isomer was a kinetic product and isomerized to its thermodynamically stable epimer in the presence of an F- anion.

Organometallic Ferrocene- and Phosphorus-Containing Polymers: Synthesis and Characterization

“…However, the boron adducts do successfully undergo thermal ROP. Miyoshi and co-workers [217,218] reported a complementary route to both the thermal and TM-catalyzed methods to afford phophorus-bridged polymers by ROP upon UV irradiation and successfully polymerized metal-bearing ferrocenophanes fcPPh[MLn] to afford the highly metalized polymers 62a-c with M w 2.2 × 10 4 and M n 2.2 × 10 4 for 62b as given in Fig. 43.…”

Strained Metallocenophanes and Related Organometallic Rings Containing π‐Hydrocarbon Ligands and Transition‐Metal Centers

“…[105,112] Strained phospha [1]ferrocenophanes 29 can also coordinate through the lone pair on phosphorus to metal fragments (Scheme 4), [113][114][115][116][117] which alternatively may insert into a PÀC bond (Scheme 5). [118,119] Stable phosphonium-bridged [1]ferrocenophanes, sulfurized P V derivatives, and borane adducts of (phenyl)phospha[1]-ferrocenophanes (31) have been prepared and in some cases and subjected successfully to thermal transition-metal-catalyzed ROP. [120,121] Notably, the enthalpies of thermal ROP recorded for (phenyl)phospha [1]ferrocenophane (29, R = Ph, À68 AE 5 kJ mol À1 ) [120] and (methylphenyl)phosphonium [1]ferrocenophane (31, R 1 = Ph, R 2 = Me, À61 AE 5 kJ mol À1 ) suggest slightly smaller strain energies than the typical values for dialkylsila [1]ferrocenophanes despite larger average tilt angles, though this is probably a consequence of the presence of the bulky phenyl substituent.…”

Reactivity of Heterodinuclear Complexes Formed by Platinum Insertion to Phosphorus-Bridged [1]Ferrocenophane Coordinating to a Metal Fragment

“…The two PMe 3 ligands on the platinum center were observed at -27.9 and -25.9 ppm, which are assigned to the PMe 3 groups cis and trans with respect to the bridging phosphido group, respectively. The structure was confirmed by X-ray analysis, as shown in Figure 2, where the W(CO) 5 and Pt(PMe 3 ) 2 fragments are connected through the ferrocenylphenylphosphido bridge in a manner similar to that found in 4. From the two reactions described above, it is found that phosphido-bridged heterodinuclear complexes can be obtained through the insertion reaction of the Pt-(PMe 3 ) 2 fragment into the P-C bond of the fcpp-metal complex (eq 5).…”

“…The reaction of 1,1′-ferrocenediylphenylphosphine (1), abbreviated as fcpp, with CpMn(CO) 2 (THF) or W(CO) 5 -(THF) gave CpMn(CO) 2 (fcpp) (2) or W(CO) 5 (fcpp) (3), respectively. 9 2 thus obtained was allowed to react with Pt(PMe 3 ) 4 in toluene at 70°C for 6 h. With silica gel column chromatography, the product was isolated in low yield, probably due to partial decomposition during the chromatography in the air, because the 31 P{ 1 H} NMR spectrum of the reaction mixture showed that an isolated species was a major product.…”

“…The thermal ellipsoids are drawn at the 50% probability level. Selected bond lengths (Å) and angles (deg): Pt1-W1, 2.7656(3); Pt1-P1, 2.264(2); Pt1-P2, 2.267(2); Pt1-P3, 2.237(2); W1-P1, 2.512(2); W1-P2, 2.493(2); P1-C1, 1.817(6); P1-C17, 1.818(7); C6-C11, 1.472(10); W1-Pt1-P1, 58.92(4); W1-Pt1-P2, 58.38(4); P1-Pt1-P2, 117.23(6); P1-Pt1-P3, 121.96(6); P2-Pt1-P3, 120.12(6); Pt1-W1-P1, 50.52(4); Pt1-W1-P2, 50.75-(4); P1-W1-P2, 101.23(5); Pt1-P1-W1, 70.55(4); Pt1-P2-W1, 70.87(5).…”