Binuclear half-sandwich cobalt(III) and rhodium(III) ortho-carboranedichalocogenolato complexes with ether chain-bridged bis(cyclopentadienyl) ligand.

1, 1'-(3-Oxapentamethylene)dicyclopentadiene [O(CH(2)CH(2)C(5)H(5))(2)], containing a flexible chain-bridged group, was synthesized by the reaction of sodium cyclopentadienide with bis(2-chloroethyl) ether through a slightly modified literature procedure. Furthermore, the binuclear cobalt(III) complex O[CH(2)CH(2)(eta(5)-C(5)H(4))Co(CO)I(2)](2) and insoluble polynuclear rhodium(III) complex {O[CH(2)CH(2)(eta(5)-C(5)H(4))RhI(2)](2)}(n) were obtained from reactions of with the corresponding metal fragments and they react easily with PPh(3) to give binuclear metal complexes, O[CH(2)CH(2)(eta(5)-C(5)H(4))Co(PPh(3))I(2)](2) and O[CH(2)CH(2)(eta(5)-C(5)H(4))Rh(PPh(3))I(2)](2), respectively. Complexes react with bidentate dilithium dichalcogenolato ortho-carborane to give eight binuclear half-sandwich ortho-carboranedichalcogenolato cobalt(III) and rhodium(III) complexes O[CH(2)CH(2)(eta(5)-C(5)H(4))Co(PPh(3))(E(2)C(2)B(10)H(10))](2) (E = S and Se), O[CH(2)CH(2)(eta(5)-C(5)H(4))](2)Co(2)(E(2)C(2)B(10)H(10)) (E = S and Se), O[CH(2)CH(2)(eta(5)-C(5)H(4))Co(E(2)C(2)B(10)H(10))](2) (E = S and Se and O[CH(2)CH(2)(eta(5)-C(5)H(4))Rh(PPh(3))(E(2)C(2)B(10)H(10))](2) (E = S and Se). All complexes have been characterized by elemental analyses, NMR spectra ((1)H, (13)C, (31)P and (11)B NMR) and IR spectroscopy. The molecular structures were determined by X-ray diffractometry.

[1]  Jian‐Qiang Wang,et al.  Porphyrin-carborane organometallic assemblies based on 1, 2-dicarba-closo-dodecaborane (12) ligands. , 2006, Chemical communications.

[2]  Jian‐Qiang Wang,et al.  Tetrametallic clusters (Ir(2)Rh(2)) through an ancillary ortho-carborane-1,2-dichalcogenolato ligands. , 2006, Dalton transactions.

[3]  G. Jin,et al.  Synthesis and structure of heterometallic complexes (RhFe, CoFe) containing bridging 1,2-dicarba-closo-dodecarborane-1,2-dichalcogenolato ligands. , 2006, Dalton transactions.

[4]  G. Jin,et al.  Olefin polymerization behavior of the cyclopentadienyl cobalt complexes bearing pendant sulfur or oxygen ligands , 2006 .

[5]  G. Jin,et al.  Heterometallic cluster complexes (RhMo, RhW) containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalocogenolato ligands. , 2006, Dalton transactions.

[6]  Shuang Liu,et al.  Synthesis of heteronuclear (MoRu2) clusters from 16-electron half-sandwich complexes (p-Cymene)Ru[E2C2(B10H10)] (E = S, Se) , 2006 .

[7]  Jian‐Qiang Wang,et al.  Synthesis and characterization of heterometallic clusters (Ir2Rh, Ir2W, Rh3) Containing 1,2-dicarba-closo-dodecaborane(12)-1,2-dithiolate chelate ligands, [(B10H10)C2S2]2-. , 2005, Chemistry.

[8]  G. Jin,et al.  Heteronuclear tungsten and cobalt derivatives of the 16-electron half-sandwich complex Cp*Rh[E2C2(B10H10)] (E = S, Se) , 2005 .

[9]  Jian‐Qiang Wang,et al.  Route to multicluster containing ancillary ortho-carborane-1,2-dithiolato ligands. , 2005, Chemical communications.

[10]  Jian‐Qiang Wang,et al.  Heteronuclear Molybdenum and Nickel Derivatives of the 16-Electron Half-Sandwich Complex Cp‘Rh[E2C2(B10H10)] (E = S, Se)† , 2005 .

[11]  G. Jin,et al.  Half-sandwich cyclopentadienyl rhodium complexes bearing pendant sulfur or oxygen ligands and their catalytic behaviors in ethylene polymerization , 2005 .

[12]  Jian‐Qiang Wang,et al.  Synthesis and Structure of Heterometallic Clusters (IrCo2, IrFe) Containing Bridging 1,2-Dicarba-closo-dodecaborane-1,2-dichalocogenolato Ligands , 2005 .

[13]  Jian‐Qiang Wang,et al.  Rational synthesis of trinuclear (WIr2) cluster from the 16-electron half-sandwich complex Cp*Ir[Se2C2(B10H10)] , 2005 .

[14]  Wei Li,et al.  Hetero-nuclear Co–W complex CpttCoW(CO)2[Se2C2(B10H10)]2 from 16-electron half-sandwich complex CpttCo[Se2C2(B10H10)] , 2004 .

[15]  Jian‐Qiang Wang,et al.  Sulfur and oxygen functionalized cyclopentadienyl half-sandwich cobalt complexes with 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligands , 2004 .

[16]  G. Jin.  Advances in the chemistry of organometallic complexes with 1,2-dichalcogenolato-o-carborane ligands , 2004 .

[17]  J. Kennedy,et al.  Polyhedral monocarbaborane chemistry. Carboxylic acid derivatives of the [closo-2-CB9H10]- anion. , 2004, Chemical communications.

[18]  Jian‐Qiang Wang,et al.  Formation of Ir-Rh and Ir-Mo bonds by using an ancillary ortho-carborane-1,2-diselenolato ligand. , 2004, Angewandte Chemie.

[19]  L. Weng,et al.  Synthesis and reaction of 16-electron CptRh halfsandwich complexes containing 1,2-dichalcogenolate carborane ligands , 2003 .

[20]  C. Mealli,et al.  Trimethylsilyl-substituted ligands as solubilizers of metal complexes in supercritical carbon dioxide , 2003 .

[21]  M. A. Fox,et al.  Intra- and inter-molecular carboranyl C–H⋯N hydrogen bonds in pyridyl-containing ortho-carboranes , 2003 .

[22]  Zuowei Xie.  Cyclopentadienyl-carboranyl hybrid compounds: a new class of versatile ligands for organometallic chemistry. , 2003, Accounts of chemical research.

[23]  L. Weng,et al.  Synthesis and Structural Characterization of Organolanthanide Complexes with 1,2-Dicarba-closo-dodecaborane-1,2-dichalcogenolate Ligands , 2002 .

[24]  Zuowei Xie.  Advances in the chemistry of metallacarboranes of f-block elements , 2002 .

[25]  Chongmok Lee,et al.  Investigation of New Coordination Modes for Coordinatively Unsaturated (Dithiolato)cobalt(III) Complex [(η5-Cp)Co(1,2-S2C2B10H10-S,S‘)] , 2002 .

[26]  J. Ko,et al.  Chemistry of o-carboranyl derivatives , 2001 .

[27]  H. Pritzkow,et al.  Nitrogen-Functionalized Cyclopentadienyl Ligands with a Rigid Framework: Complexation Behavior and Properties of Cobalt(I), -(II), and -(III) Half-Sandwich Complexes , 2001 .

[28]  J. Ko,et al.  Steric Influence on the Reactivity of the (o-Carboranedithiolato)iridium(III) Complex [Ir(η5-C5Me5)(η2-S2C2B10H10)]: New Types of Addition Reactions Involving Cyclometalation or Isomerization† , 2000 .

[29]  M. Hawthorne,et al.  Applications of Radiolabeled Boron Clusters to the Diagnosis and Treatment of Cancer. , 1999, Chemical reviews.

[30]  G. Jin,et al.  16- and 18-Electron Cp*Rh complexes with 1,2-dicarba-closo-dodecaborane(12)-1,2-dichalcogenolato ligands, as studied by multinuclear magnetic resonance , 1999 .

[31]  J. Ko,et al.  Addition Reactions of the Novel Mononuclear Dithio-o-carboranylcobalt(III) Complex (η5-C5H5)Co(η2-S2C2B10H10) , 1999 .

[32]  J. Ko,et al.  Synthesis, X-ray crystal structure, and reactivity of the monomeric dithio-o-carboranyl iridium complex [Ir(η5-C5Me5)(η2-S2C2B10H10)] , 1999 .

[33]  B. Neumüller,et al.  TRIMETHYLGALLIUM-INDUCED TRIMERIZATION OF ACETONITRILE , 1998 .

[34]  M. Hawthorne,et al.  Recognition of Electron-Donating Guests by Carborane-Supported Multidentate Macrocyclic Lewis Acid Hosts: Mercuracarborand Chemistry , 1997 .

[35]  Gautam R. Desiraju,et al.  Supramolecular Synthons in Crystal Engineering—A New Organic Synthesis , 1995 .

[36]  V. I. Bregadze,et al.  Dicarba-closo-dodecaboranes C2B10H12 and their derivatives , 1992 .

[37]  Jaromir Plesek,et al.  Potential applications of the boron cluster compounds , 1992 .

[38]  A. R. Manning,et al.  The reaction of [{Co(CO)2(η5-C5H4)}2CH2] with iodine and mercuric halides , 1990 .

[39]  H. Werner,et al.  Bis(cyclopentadienyl)methan-verbrückte Zweikernkomplexe: II. Synthese und Reaktionen ringverbrückter Cobalt-Zweikernkomplexe mit zwei nucleophilen Metallzentren , 1989 .

[40]  C. Qian,et al.  Studies on organolanthanide complexes. XII: Synthesis, identification and reactivity of organolanthanide and -yttrium chlorides with the chelating 1,1'-(3-oxa-pentamethylene)dicyclopentadienyl ligand , 1987 .

[41]  M. A. White,et al.  Carbon-carbon bond formation in dinuclear dialkyl complexes. Reactions of [CpCo(CO)R]2 (R = methyl, ethyl, or 2,2,2-trifluoroethyl) and (C11H10)Co2(CO)2(CH3)2 with carbon monoxide and triphenylphosphine , 1984 .

[42]  H. Yamazaki,et al.  Preparations and reactions of alkylcobalt complexes and diphenylacetylenecobalt complexes having a π-cyclopentadienyl group as a ligand , 1970 .

[43]  R. King.  Organometallic Chemistry of the Transition Metals. XI. Some New Cyclopentadienyl Derivatives of Cobalt and Rhodium , 1966 .

[44]  J. Chatt,et al.  955. Olefin co-ordination compounds. Part VI. Diene complexes of rhodium(I) , 1957 .