Reaction of phosphorus-bridged ferrocenophane Fe(.eta.5-C5H4PPh)(.eta.5-C5H4) with LiC5H5 and NaFe(CO)2(.eta.5-C5H5). Structures of {Fe[(.eta.5-C5H4)2]P(C6H5)-P}Fe(H)(.eta.5-C5H5)(CO) and {(C6H5)[Fe(.eta.5-C5H5)(.eta.5-C5H4)][Fe(.eta.5-C5H5)(.eta.5-C5H3C(O))]P-P,C}Fe(.eta.5-C5H5)(CO).cntdot.CHCl3

Abstract

No. [H2Et2][HFe3(CO)n], 2N][HFe3(CO)u], 107011-15-4; [H2(i-Pr)2N][HFe3(CO)n], 107011-16-5; [PPN][HFe3(CO)nJ, 23254-21-9; [HEt3N][HFe3-(CO)u], 56048-18-1; K[HFe3(CO)n], CO, Supplementary Material Available: Table IV, fractional coordinates (X104) for the hydrogen atoms of [H2(z-Pr)2][HFe3-(CO)u], and Table V, anisotropic temperature factors of [H2(t-Pr)2N][HFe3(CO)u] (2 pages); Table VI, observed and calculated structure factors (14 pages). Ordering information is given on any current masthead page.Reaction of Fe(7/5-C5H4PPh) (ij5 c5H4) with LICSHS and NaFe(CO)2(»;5-C5H5). Structures of |Fe[(7,5-C5H4)2]P(CeH5)-P¡Fe(H)(7,5-C5H5)(CO) and ¡(CeH5)[Fe(7,s-C5H5)(^5-C5H4)][Fe(^5-C5H5)(^-C5H3C(0))]P-P,ClFe(ij5-C5H5)(CO)-CHCI3

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

“…The dihedral angle, α, is 25.0°, which is comparable to the value of 26.9° for the free ligand FCPP 2a. It is thus confirmed that the strain of the [1]ferrocenophane unit is almost intact when FCPP coordinates to a metal, as previously described for [Cp(CO)HFe(FCPP)] ( 3 ), in which α is 25.4° give us an interesting structural feature of the phosphorus-bridged [1]ferrocenophane.…”

“…Since the ferrocenophane has lone-pair electrons on the phosphorus, it may serve as a ligand toward a transition metal. Several complexes ( 1 − 4 ) 1b, possessing a phosphorus-bridged [1]ferrocenophane as a ligand have been synthesized. However, their reactivities have not yet been examined.…”

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

“…[110,111] High-molecular-weight material can also be obtained by thermal ROP and, as shown by Miyoshi and co-workers, by photoirradiation in THF. [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.…”

Gespannte Metallocenophane und ähnliche metallorganische Ringe mit π‐Kohlenwasserstoffliganden und Übergangsmetallzentren

“…Polymere mit hohem Molekulargewicht werden auch bei der thermischen ROP erhalten, und, wie Miyoshi und Mitarbeiter zeigten, auch durch Bestrahlen in THF 105. 112 Die gespannten Phospha[1]ferrocenophane 29 können über das freie Elektronenpaar des Phosphoratoms an weitere Metallfragmente koordinieren (Schema ),113–117 die auch in die P‐C‐Bindung inserieren können (Schema ) 118. 119 Stabile phosphoniumverbrückte [1]Ferrocenophane, sulfurierte Phosphor(V)‐Derivate und Boranaddukte von Phenylphospha[1]ferrocenophanen ( 31 ) wurden hergestellt, und mit einigen gelang eine thermisch ausgelöste übergangsmetallkatalysierte ROP 120.…”