Phosphorus- and arsenic-bridged [1]ferrocenophanes. 1. Synthesis and characterization

Seyferth, Dietmar; Withers, Howard P.

doi:10.1021/om00070a004

Cited by 133 publications

(47 citation statements)

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“…Another specific approach, is the ring opening with phenyllithium of the strained 1-phenyl-1-phospha-[1]-ferrocenophane 6, which can be obtained from the corresponding 1,1′-dilithiated ferrocene 1 (Scheme 2) [22][23][24][25]. When this compound is now reacted with N,Ndimethylformamide, the corresponding phosphane ferrocenecarbaldehyde 8 is formed.…”

Section: Synthetic Routes Towards Chiral 11′-disubstituted Pn-ferromentioning

confidence: 99%

Ferrocene-derived P,N ligands: synthesis and application in enantioselective catalysis

Noël¹,

Eycken²

2013

Green Processing and Synthesis

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Due to their unique steric and electronic properties, air-stability and modular structure, chiral hybrid P,N-ferrocenyl ligands play a prominent role in the field of asymmetric catalysis. This report aims to give a concise introduction to the syntheses of chiral hybrid P,N-ferrocenyl ligands and presents an overview of their application in enantioselective catalysis. This review is of special interest to chemists working on ligand design and asymmetric catalysis, as well as to the broader organic and inorganic community.

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Section: Synthetic Routes Towards Chiral 11′-disubstituted Pn-ferromentioning

confidence: 99%

Ferrocene-derived P,N ligands: synthesis and application in enantioselective catalysis

Noël¹,

Eycken²

2013

Green Processing and Synthesis

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“…[103] The similarities between phosphorus-bridged [1]ferrocenophanes are manifested in the narrow range of a angles (26.9-27.98). [6,7,23,[103][104][105][106][107] The single example of a structurally characterized arsa [1]ferrocenophane 30 (R 1 = CH(Me)NMe 2 ) contains more tilted cyclopentadienyl rings (a = 22.98) than expected given the larger covalent radius of arsenic. [23] The similarities between As-and P-bridged [1]ferrocenophanes are much more pronounced than between As-and Ge-bridged derivatives despite their nearly identical covalent radii (P 1.10 ; As 1.21 ; Ge 1.22 ).…”

Section: Ansa Complexesmentioning

confidence: 99%

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

2007

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The structures, bonding, and ring-opening reactions of strained cyclic carbon-based molecules form a key component of standard textbooks. In contrast, the study of strained organometallic molecules containing transition metals is a much more recent development. A wealth of recent research has revealed fascinating nuances in terms of structure, bonding, and reactivity. Building on initial work on strained ferrocenophanes, a broad range of strained organometallic rings composed of a variety of different metals, pi-hydrocarbon ligands, and bridging elements has now been developed. Such strained species can potentially undergo ring-opening reactions to functionalize surfaces and ring-opening polymerization to form easily processed metallopolymers with properties determined by the presence of the metal and spacer. This Review summarizes the current state of knowledge on the preparation, structural characterization, electronic structure, and reactivity of strained organometallic rings with pi-hydrocarbon ligands and d-block metals.

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“…[19] and by Seyferth and co-workers. [12] A further significant contribution in this area was reported shortly thereafter by Cullen. [20] The phosphorus-bridged [1]ferrocenophane 1 was prepared by following a similar procedure to that reported by Cullen and co-workers by using the commercially available tert-butyldichlorophosphine.…”

Section: Resultsmentioning

confidence: 87%

“…As reported previously, polyferrocenylphosphines do not elute from the GPC column when using THF as the eluent, as they interact with the column material, presumably due to the Lewis basicity of the P III center. [12,13] For that reason, the polymers with P III sites of polyferrocenylphosphines were sulfurized, resulting in the formation of the corresponding poly(ferrocenylphosphine sulfides), which eluted easily through GPC columns. [23] The proposed mechanism of the photolytic living anionic ROP of 1-3 is shown in Scheme 6.…”

Section: Resultsmentioning

confidence: 99%

“…The first PFP, polyferrocenylphenylphosphine, was prepared by a condensation route from [FeA C H T U N G T R E N N U N G (h-C 5 H 4 Li) 2 ] and PhPCl 2 in 1982. [12] Although several polymerization routes, such as thermal [13] and anionic ROP, [11] have subsequently been developed to access PFPs, the synthesis of well-defined and high molecular weight PFPs still represents a considerable synthetic challenge. Living anionic polymerization initiated by organolithium reagents proceeds by cleavage of a phosphorus-cyclopentadienyl (PÀCp) bond in the monomer.…”

Section: Introductionmentioning

confidence: 99%

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Photocontrolled Living Anionic Polymerization of Phosphorus‐Bridged [1]Ferrocenophanes: A Route to Well‐Defined Polyferrocenylphosphine (PFP) Homopolymers and Block Copolymers

Patra

Whittell

Nagiah

et al. 2010

Chemistry A European J

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Phosphorus-bridged strained [1]ferrocenophanes [Fe{(eta-C(5)H(4))(2)P(CH(2)CMe(3))}] (2) and [Fe{(eta-C(5)H(4))(2)P(CH(2)SiMe(3))}] (3) with neopentyl and (trimethylsilyl)methyl substituents on phosphorus, respectively, have been synthesized and characterized. Photocontrolled living anionic ring-opening polymerization (ROP) of the known phosphorus-bridged [1]ferrocenophane [Fe{(eta-C(5)H(4))(2)P(CMe(3))}] (1) and the new monomers 2 and 3, initiated by Na[C(5)H(5)] in THF at 5 degrees C, yielded well-defined polyferrocenylphosphines (PFPs), [Fe{(eta-C(5)H(4))(2)PR}](n) (R=CMe(3) (4), CH(2)CMe(3) (5), and CH(2)SiMe(3) (6)), with controlled molecular weights (up to ca. 60 x 10(3) Da) and narrow molecular weight distributions. The PFPs 4-6 were characterized by multinuclear NMR spectroscopy, DSC, and by GPC analysis of the corresponding poly(ferrocenylphosphine sulfides) obtained by sulfurization of the phosphorus(III) centers. The living nature of the photocontrolled anionic ROP allowed the synthesis of well-defined all-organometallic PFP-b-PFS(F) (7a and 7b) (PFS(F)=polyferrocenylmethyl(3,3,3,-trifluoropropyl)silane) diblock copolymers through sequential monomer addition. TEM studies of the thin films of the diblock copolymer 7b showed microphase separation to form cylindrical PFS(F) domains in a PFP matrix.

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Phosphorus- and arsenic-bridged [1]ferrocenophanes. 1. Synthesis and characterization

Cited by 133 publications

References 0 publications

Ferrocene-derived P,N ligands: synthesis and application in enantioselective catalysis

Ferrocene-derived P,N ligands: synthesis and application in enantioselective catalysis

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

Photocontrolled Living Anionic Polymerization of Phosphorus‐Bridged [1]Ferrocenophanes: A Route to Well‐Defined Polyferrocenylphosphine (PFP) Homopolymers and Block Copolymers

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