Ferrocyne and ferrodicyne. Preparation and structures of Os3(CO)s[.mu.3-(C5H3)Fe(C5H5)][.mu.3-P(C5H4)Fe(C5H5)], Os3(H)2(CO)8(PPr-iso2C5H2)Fe(C5H2PPr-iso2)Os3(H)2(CO)8, and Os3(CO)9[.mu.3-C6H4][.mu.3-P(C5H4)Fe(C5H5)]

Cullen, William R.; Rettig, Steven J.; Zheng, Tu Cai

doi:10.1021/om00038a064

Cited by 37 publications

(5 citation statements)

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“…In particular, 1-chloro-2-lithioferrocene is quite stable at −15 °C whereas chlorobenzene has to be deprotolithiated at about −100 °C to avoid benzyne formation . On the basis of the calculated p K a values for both 2-halogenoferrocenes and -benzenes (see Figure , left), one might suggest that the instability of 2-halogenoferrocenyllithiums is not at the origin of ferrocyne formation. , …”

supporting

confidence: 89%

Fluoro- and Chloroferrocene: From 2- to 3-Substituted Derivatives

et al. 2018

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supporting

confidence: 89%

Fluoro- and Chloroferrocene: From 2- to 3-Substituted Derivatives

et al. 2018

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“…According to our interest in 1,2‐dehydroferrocene (“ferrocyne”) and 1,2,1′,2′‐tetradehydroferrocene (“ferrocenediyne”) we recently reported the formation of 2‐(trifluoromethylsulfonyl)ferrocenols by unprecedented anionic thia‐Fries rearrangements of ferrocenyl triflates under mild reaction conditions in high yields instead of the desired elimination products , . An osmium complex with 1,2‐dehydroferrocene as a ligand has been reported by Cullen et al as early as in 1992 . Herein, we report new or significantly improved syntheses of 1,2‐dihaloferrocenes as well as ferrocenecarboxylic acid derivatives obtained by ortho ‐lithiation.…”

Section: Introductionmentioning

confidence: 99%

Improved Syntheses of 1,2‐Disubstituted Ferrocenes

Werner

Butenschön

2016

Eur J Inorg Chem

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1,2-Disubstituted ferrocenes, in particular 1,2-dihaloferrocenes, are important starting materials. Herein, we describe significantly improved high-yielding syntheses of 1,2-disubstituted ferrocenes such as 1,2-dibromo-and 1,2-diiodoferrocene as well as 1-bromo-2-iodoferrocene, and 1-bromo-2-fluoroferrocene. DFT calculations show that 1,2-dihaloferrocenes do not differ much in their highest occupied molecular orbital (HOMO) energies; however, their lowest unoccupied molecular orbital (LUMO) energies -and thus the HOMO/LUMO gaps -correlate

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“…Complex 2 can thus be viewed as two heterometallic AuMn 2 triangles singly bridged by dppf. This concept of linked clusters has been described elsewhere in which ligands (“fillers”) are used to link two identical or different cluster fragments . Complex 2 is, however, the only example of heterometallic clusters which are joined similarly.…”

Section: Resultsmentioning

confidence: 99%

Substituted Metal Carbonyls. 27.¹ Synthesis, Structures, and Metal−Metal Bonding of a Ferrocenylphosphine exo-Bridged Cluster with Two Heterometallic Triangles, [AuMn₂(CO)₈(μ-PPh₂)]₂(μ-dppf), and a Twisted-Bowtie Cluster, PPN⁺[Au{Mn₂(CO)₈(μ-PPh₂)}₂]^- (dppf = 1,1‘-Bis(diphenylphosphino)ferrocene)

Low¹,

Tan²,

Hor³

et al. 1996

Organometallics

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Redox condensation of PPN[Mn2(CO)8(μ-PPh2)] (1; (PPN = N(PPh3)2) with Au2Cl2(μ-P−P) (P−P = (C5H4PPh2)2Fe (dppf), Ph2PC2H4PPh2 (dppe)) gives two hexanuclear Au−Mn clusters [AuMn2(CO)8(μ-PPh2)]2(μ-P−P) (P−P = dppf, (2), dppe (4)), both of which contain a diphosphine bridging two Mn2Au triangles. Complex 2 is formed via an intermediate, AuCl(μ-dppf)[AuMn2(CO)8(μ-PPh2)], (3), which was isolated. Bridge cleavage of 2 occurs at thf reflux with PPh3 and room temperature with P(OEt)3 to give the triangular clusters [(PR3)AuMn2(CO)8(μ-PPh2)] (R = Ph (5), OEt (6)), respectively. The latter exchange of dppf with P(OEt)3 is reversible in solution. Condensation of 1 with AuCl(SMe2) gives an anionic pentanuclear cluster, PPN[Au{Mn2(CO)8(μ-PPh2)}2] (7). Complexes 2 and 7 were structurally characterized by single-crystal X-ray diffractometry. Complex 2, which is centrosymmetric with Fe in dppf at a crystallographic inversion center, consists of a ferrocenylphosphine bridging two heterometallic triangles (Au−Mn = 2.660(1) and 2.776(1) Å; Mn−Mn = 3.049(2) Å). Complex 7 is made up of two planar AuMn2P metallacycles fused at Au at an angle of 85.50(4)°. With crystallographic C 2 symmetry, a twisted-bowtie skeleton resulted with gold at its center. Both Au−Mn (mean 2.806(1) Å) and (PPh2-bridged) Mn−Mn (3.105(2) Å) lengths are significantly longer than those in 2. The Mn−Mn bond of 2 is also significantly longer than that of 1. Fenske−Hall MO calculations on 1, 2, and 7 together with Mn2(CO)8(μ-H)(μ-PPh2) (8) and (PPhMe2)AuMn2(CO)8(PPh2) (9) indicate that aside from 1, all the complexes, including 2 and 7, give a negative overlap population in the Mn−Mn interactions. The Mn−Mn distance appears to be determined by the strength of the AuMn2 interaction and/or the size of H compared to Au. The weaker Mn−Mn and Au−Mn interactions in 7 (as compared to those in 2 and 9, respectively) are likely to be caused by the absence of Au orbital reinforcement in the direction of the Mn2 moiety as a consequence of symmetry.

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Ferrocyne and ferrodicyne. Preparation and structures of Os3(CO)s[.mu.3-(C5H3)Fe(C5H5)][.mu.3-P(C5H4)Fe(C5H5)], Os3(H)2(CO)8(PPr-iso2C5H2)Fe(C5H2PPr-iso2)Os3(H)2(CO)8, and Os3(CO)9[.mu.3-C6H4][.mu.3-P(C5H4)Fe(C5H5)]

Cited by 37 publications

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Fluoro- and Chloroferrocene: From 2- to 3-Substituted Derivatives

Fluoro- and Chloroferrocene: From 2- to 3-Substituted Derivatives

Improved Syntheses of 1,2‐Disubstituted Ferrocenes

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