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Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/12814

Title: Cyclodiphosphazane cis-{(o-MeOC6H4O)P(mu-NtBu)}(2) as a bridging bidentate ligand: Synthesis, structures of heterometallic complexes, and halogen exchange between Rh-Cl and Cu-X (X = Br, I)
Authors: CHANDRASEKARAN, P
MAGUE, JT
VENKATESWARAN, R
BALAKRISHNA, MS
Keywords: transition-metal-complexes
late heterobimetallic complexes
coordination chemistry
molecular-structures
catalytic-activity
electrochemical oxidation
homogeneous hydrogenation
reversible conversion
magnetic-properties
building-block
Issue Date: 2007
Publisher: WILEY-V C H VERLAG GMBH
Citation: EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, (31), 4988-4997
Abstract: The mononuclear rhodium complexes of cyclodiphosphazane [(cod)RhCl{L-kappa P}] (1a) (L = cis-{(o-MeOC6H4O)P(mu- NtBu)}(2)) and trans- [Rh(CO)Cl{L-kappa P}(2)] (1b) react in a 1:1 molar ratio with [AuCl(SMe2)] to form the heteronuclear complexes [(cod)RhCl{mu-L-kappa P,kappa P)AuCl] (2) and trans-[Rh(CO)-Cl{mu-L-kappa P,kappa P)(2)}(AuCl] (2) (7), respectively, in quantitative yield. The reaction between la and CuCl afforded a tetranuclear complex [(cod)RhCl{mu-L-kappa P,kappa P}Cu(mu-Cl)](2) (3). Under similar reaction conditions 1 reacts with 2 equiv. of CuX (X = Br, I) to produce the heteronuclear complexes [(cod)RhBr{mu-L-kappa P,kappa P}Cu(mu-Br)](2) (4) and [((cod)RhI{mu-L-kappa P,kappa P})2Cu(mu-X)(2)Cu] (X 1:1 mixture of Cl and I disordered over both sites) (5), respectively, in which two molecules of la are bridged by the rhombic, disordered, mixed halide[Cu(mu-X)(2)Cu] (5: X = Br; 6: X = Cl, I) unit. The crystal structures of 4 and 5 confirm the halogen exchange between the Rh-Cl and CuX (X = Br, 1) moieties which leads to the formation of Rh-Br and Rh-I bonds. The heterodinuclear Rh-I/Pd-II complex [(cod)RhCl{mu-L-kappa P,kappa P)PdCl(eta(3)- C3H5)] (6) was synthesized by the reaction of la with [PdCl(eta(3)-C3H5)](2) in a 2:1 ratio. Reaction of 1b with CuI leads to the formation of the tetranuclear complex [Rh(CO)I{mu-L-kappa P,kappa P}(2)Cu(mu I)](2) (8) containing two terminal uncoordinated phosphorus(III) centers irrespective of reactant ratio and reaction conditions. Halogen exchange reaction which leads to the formation of the Rh-I bond was also observed during the preparation of complex 8. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
URI: http://dx.doi.org/10.1002/ejic.200700554
http://dspace.library.iitb.ac.in/xmlui/handle/10054/12814
http://hdl.handle.net/10054/12814
ISSN: 1434-1948
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