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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 15, Number 11
BKCSDE 15(11)
November 20, 1994 

Synthesis and Reaction Chemistry of Some Ferrocene-Containing Chelate Ligands with Dirhodium Acetate : X-ray Crystal Structure of (η1-(S,R)-CPFA)2Rh2(OAc)4
Eun-Jin Kim, Tae-Jeong Kim*
New ferrocene-based chelate amines, Fe[C5H4CH(Me)NMe2]2 (3), Fe[C5H3(CH(Me)NMe2)(PPh2)-1,2]2 (4), (C5H5)Fe(C5H3(CH2NMe2)(CH(CN)NMe2-1,2) (6), and (C5H5)Fe(C5H3(CH2NMe2)(CH(Me)NMe2-1,2) (7) have been prepared. The reaction and the coordination chemistry of 4 and other related compounds (S,R)-(1-N,N-dimethylaminoethyl)-2-dicyclohexylph osphino)ferrocene (CPFA) and 1,1'-bis-(diphenylphosphino)ferrocene (BPPF) with Rh2(OAc)4(MeOH)2 were investigated. The reaction of the chiral ligand (S,R)-CPFA forms a complex of the type (η1-(S,R)-CPFA-P)2Rh2(OAc)4 (8) in which the ligand is coordinated to both rhodium centers in a monodentate fashion through phosphorus. In contrast, the bisphosphine analogues such as BPPF and 4 afford chelate complexes of the type (η2-PP)Rh2(OAc)4 (9 & 10) where both ligands act as a chelate bidentate to a single rhodium atom. All these complexes were characterized by microanalytical and spectroscopic techniques. In one case, the structure of 8 was determined by X-ray crystallography. Crystals are monoclinic, space group C2 (No. 5), with a=26.389 (3), b=12.942 (1), c=11.825 (1) A, β=111.22(1)°, V=3964.7 (8) A3, Z=4, and Dcalc=1.58 g cm-3. Two Rh(Ⅱ) centers are bridged by four AcO- groups in the η1 : η1 mode across a Rh-Rh single bond, and octahedral coordination at Rh(1) and Rh(1') is completed by axially coordinating (S,R)-CPFA and a briding AcO-, respectively.
990 - 996
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