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Thioether-functionalized ferrocenyl-bis(phosphonite), Fe{(C5H4)P(-OC10H6(mu-S)C10H6O-)}(2): Synthesis, coordination behavior, and application in suzuki-miyaura cross-coupling reactions

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Title Thioether-functionalized ferrocenyl-bis(phosphonite), Fe{(C5H4)P(-OC10H6(mu-S)C10H6O-)}(2): Synthesis, coordination behavior, and application in suzuki-miyaura cross-coupling reactions
 
Creator PUNJI, B
MAGUE, JT
BALAKRISHNA, MS
 
Subject transition-metal chemistry
catalyzed allylic substitutions
chiral ferrocenyl phosphines
cu-i interaction
structural-characterization
asymmetric catalysis
x-ray
heterogeneous catalysis
reversible conversion
homogeneous catalysis
 
Description The thioether-functionalized metalloligand ferrocenyl-bis(phosphonite), Fe(C5H4PR)(2) (4, R = -OC(10)oH(6)(mu-S)C10H6O-) is synthesized in three steps starting from ferrocene, and its coordination behavior toward various transition-metal derivatives is described. The reactions of 4 with [Rh(CO)(2)Cl](2) or M(COD)Cl-2 afforded the chelate complexes, cis-[Rh(CO)Cl{Fe(C5H4PR)(2)-kappa P,kappa P}] (5) or cis-[MCl2{Fe(C5H4PR)(2)-kappa P kappa P}] (6, M = Pd-II; 7, M = Pt-II), respectively. However, treatment of 4 with CuX (X = Cl, Br, and 1) produces binuclear complexes, [CU2(mu-X)(2)(MeCN){Fe(C5H4PR)(2)-kappa P,kappa P}] (8, X = Cl; 9, X = Br; 10, X = I) where the sulfur atom on one side of the ligand is involved in a weak interaction with the copper center. Reaction of 4 with 1 equiv of Ag(PPh3)OTf gives the mononuclear chelate complex [Ag(OTf)PPh3{Fe(C5H4PR)(2)-kappa P kappa P}] (11), whereas treatment with 2 equiv of AuCl(SMe2) produces the dinuclear gold complex [Au(Cl){Fe(C5H4PR)(2)-kappa P kappa P}Au(Cl)] (12). The crystal structures of 10 and 12 are reported, where a strong metallophilic interaction is observed between the closed-shell metal centers. The palladium complex 6 catalyzes the Suzuki cross-coupling reactions of aryl bromides with phenylboronic acid with excellent turnover numbers (TON up to 1.36 x 10(5)).
 
Publisher AMER CHEMICAL SOC
 
Date 2011-07-15T02:50:56Z
2011-12-26T12:49:12Z
2011-12-27T05:34:59Z
2011-07-15T02:50:56Z
2011-12-26T12:49:12Z
2011-12-27T05:34:59Z
2007
 
Type Article
 
Identifier INORGANIC CHEMISTRY, 46(24), 10268-10275
0020-1669
http://dx.doi.org/10.1021/ic701537k
http://dspace.library.iitb.ac.in/xmlui/handle/10054/4134
http://hdl.handle.net/10054/4134
 
Language en