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Synthesis, transition metal chemistry and catalytic reactions of ferrocenylbis(phosphonite), [Fe{C5H4P(OC6H3(OMe-o)(C3H5-p))(2)}(2)]

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Title Synthesis, transition metal chemistry and catalytic reactions of ferrocenylbis(phosphonite), [Fe{C5H4P(OC6H3(OMe-o)(C3H5-p))(2)}(2)]
 
Creator RAO, S
MAGUE, JT
BALAKRISHN, MS
 
Subject CROSS-COUPLING REACTIONS
CHIRAL FERROCENYL PHOSPHINES
ASYMMETRIC CATALYSIS
X-RAY
COPPER(I) COMPLEXES
CRYSTAL-STRUCTURE
1,1-BIS(DIPHENYLPHOSPHINO)FERROCENE DPPF
STRUCTURAL-CHARACTERIZATION
PALLADIUM COMPLEXES
II COMPLEXES
 
Description The new metalloligand ferrocenylbis(phosphonite), [Fe(C5H4PR2)(2) (R = OC6H3(OMe-o)(C3H5-p))], (2), is synthesized by the reaction of bis(dichlorophosphino)ferrocene Fe(C5H4PCl2)(2) (1) with 4-allyl-2-methoxyphenol. The reactions of 2 with H2O2 and elemental sulfur or selenium afforded bischalcogenides, [Fe{C5H4P(E)(OC6H3(OMe-o)(C3H5-p))(2)}(2)] (3, E = O; 4, E = S; 5, E = Se), in good yield. The bis(phosphonite) reacts with group 6 metal carbonyls and group 10 metal dichloride precursors to produce the chelate complexes [{M(CO)(4)}Fe{C5H4P(OC6H3(OMe-o)(C3H5-p))(2)}(2)}] (6, M = Mo; 7, M = W) and [(MCl2)Fe{C5H4P-(OC6H3(OMe-o)(C3H5-p))(2)}(2)] (8, M = Pd; 9, M = Pt). The palladium(II) complex [(PdCl2)Fe{C5H4P-(OC6H3(OMe-o)(C3H5-p))(2)}(2)] (8) is an efficient catalyst for the Suzuki-Miyaura cross-coupling reactions (TON up to 1.5 x 10(5)). The reaction of 2 with one equivalent of [RuCl2(eta(6)-p-cymene)](2) yielded the binuclear complex [{Ru2Cl4(eta(6)-p-cymene)(2)}Fe{C5H4P(OC6H3(OMe-o)(C3H5-p))(2)}(2)] (12) in good yield. Treatment of 2 with copper chloride in a 1 : 1 or 1 : 2 molar ratio resulted in the formation of a binuclear complex, [{(CuCl)Fe{C5H4P(OC6H3(OMe-o)(C3H5-p))(2)}(2)}(2)] (13), whereas a similar reaction of 2 with CuBr and CuI in a 1 : 2 or 1 : 2.5 molar ratio yielded the novel butterfly-like deca-nuclear complexes [Cu-5(mu-X)(5){Fe{C5H4P-(OC6H3(OMe-o)(C3H5-p))(2)}(2)}(2)](2) (14, X = Br; 15, X = I). The reaction of 2 with two equivalents of [AuCl(SMe2)] afforded the digold complex [(AuCl)(2)Fe{C5H4P(OC6H3(OMe-o)(C3H5-p))(2)}(2)] (16), with the ligand exhibiting bridged-bidentate mode of coordination. Additionally, some complexes were studied by cyclic voltammetry. The crystal structures of complexes 8, 9, 12, 15 and 16 were determined using X-ray diffraction studies.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2014-10-15T12:04:26Z
2014-10-15T12:04:26Z
2013
 
Type Article
 
Identifier DALTON TRANSACTIONS, 42(32)11695-11708
http://dx.doi.org/10.1039/c3dt50995h
http://dspace.library.iitb.ac.in/jspui/handle/100/14858
 
Language en