Palladium-Catalyzed Coupling of Ethynylated p-Carborane Derivatives: Synthesis and Structural Characterization of Modular Ethynylated p-Carborane Molecules
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- 作者：Wei Jiang ; David E. Harwell ; Mark D. Mortimer ; Carolyn B. Knobler ; and M. Frederick Hawthorne
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：July 17, 1996
- 年：1996
- 卷：35
- 期：15
- 页码：4355 - 4359
- 全文大小：131K
- 年卷期：v.35,no.15(July 17, 1996)
- ISSN：1520-510X
文摘
Methodology leading to a new class of rodlikep-carborane derivatives is described, involving thepalladium-catalyzed coupling of B-iodinated p-carboranes with terminalalkynes. The products of these reactions containan alkyne substituent at a boron vertex of the p-carboranecage. Reaction ofcloso-2-I-1,12-C2B10H11(1) withcloso-2-(C
ntities/tbd1.gif">CH)-1,12-C2B10H11(3) in the presence of pyrrolidine and catalytic quantitiesof bis(triphenylphosphine)palladium dichloride and cupric iodide yields1,2-(closo-1',12'-C2B10H11-2'-yl)2acetylene (4). Oxidative couplingof 3 in the presence of cupric chloride in piperidineaffords1,4-(closo-1',12'-C2B10H11-2'-yl)2-1,3-butadiyne(5).Reaction of 2 molar equiv. ofcloso-2,9-I2-1,12-C2B10H10(6) withcloso-2,9-(Cntities/tbd1.gif">CH)2-1,12-C2B10H10(7) in thepresence of pyrrolidine and catalytic quantities ofbis(triphenylphosphine)palladium dichloride and cupriciodideyieldscloso-2,9-(closo-2'-I-9'-Cntities/tbd1.gif">C-1',12'-C2B10H10)2-1,12-C2B10H10(8), a rigid, iodine-terminated carborod trimerin which the p-carborane cages are linked at the 2 and 9B-vertices by alkyne (Cntities/tbd1.gif">C) bridges. The molecularstructures of 5 and the previously describedcloso-2,9-(Cntities/tbd1.gif">CSiMe3)2-1,12-C2B10H10(9) have been determined byX-ray crystallography. Crystallographic data are as follows: for5, monoclinic, space group P2/a,a = 12.352(6)Å, b = 14.169 (6) Å, c = 12.384(5) Å,
= 109.69(2)ntities/deg.gif">, V = 2041 Å3,Z = 4, R = 0.098,Rw = 0.135; for9,monoclinic, space group C2/m, a =22.111(4) Å, b = 7.565(2) Å, c =6.943(2) Å, = 107.871(8)ntities/deg.gif">, V =1105Å3, Z = 2, R = 0.059,Rw =0.090.
ntities/tbd1.gif">CH)-1,12-C2B10H11(3) in the presence of pyrrolidine and catalytic quantitiesof bis(triphenylphosphine)palladium dichloride and cupric iodide yields1,2-(closo-1',12'-C2B10H11-2'-yl)2acetylene (4). Oxidative couplingof 3 in the presence of cupric chloride in piperidineaffords1,4-(closo-1',12'-C2B10H11-2'-yl)2-1,3-butadiyne(5).Reaction of 2 molar equiv. ofcloso-2,9-I2-1,12-C2B10H10(6) withcloso-2,9-(Cntities/tbd1.gif">CH)2-1,12-C2B10H10(7) in thepresence of pyrrolidine and catalytic quantities ofbis(triphenylphosphine)palladium dichloride and cupriciodideyieldscloso-2,9-(closo-2'-I-9'-Cntities/tbd1.gif">C-1',12'-C2B10H10)2-1,12-C2B10H10(8), a rigid, iodine-terminated carborod trimerin which the p-carborane cages are linked at the 2 and 9B-vertices by alkyne (Cntities/tbd1.gif">C) bridges. The molecularstructures of 5 and the previously describedcloso-2,9-(Cntities/tbd1.gif">CSiMe3)2-1,12-C2B10H10(9) have been determined byX-ray crystallography. Crystallographic data are as follows: for5, monoclinic, space group P2/a,a = 12.352(6)Å, b = 14.169 (6) Å, c = 12.384(5) Å, = 109.69(2)ntities/deg.gif">, V = 2041 Å3,Z = 4, R = 0.098,Rw = 0.135; for9,monoclinic, space group C2/m, a =22.111(4) Å, b = 7.565(2) Å, c =6.943(2) Å, = 107.871(8)ntities/deg.gif">, V =1105Å3, Z = 2, R = 0.059,Rw =0.090.