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Chemistry of a new trispyrazolylbora...

Yaman, Gulsah.

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Chemistry of a new trispyrazolylborate ligand with some group 1 group 2 ions.

紀錄類型:	書目-語言資料,印刷品 : Monograph/item
正題名/作者:	Chemistry of a new trispyrazolylborate ligand with some group 1 group 2 ions./
作者:	Yaman, Gulsah.
面頁冊數:	219 p.
附註:	Adviser: Malcolm H. Chisholm.
Contained By:	Dissertation Abstracts International68-12B.
標題:	Chemistry, Inorganic. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3292726
ISBN:	9780549362968

Chemistry of a new trispyrazolylborate ligand with some group 1 group 2 ions.
Yaman, Gulsah.

Chemistry of a new trispyrazolylborate ligand with some group 1 group 2 ions. - 219 p.

Adviser: Malcolm H. Chisholm.

Thesis (Ph.D.)--The Ohio State University, 2008.

All of the compounds have been characterized by elemental analysis, NMR spectroscopy, and by single-crystal X-ray studies, the latter of which reveal the versatile modes of binding for this new ligand bearing hemilabile ether appendages.

ISBN: 9780549362968Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Chemistry of a new trispyrazolylborate ligand with some group 1 group 2 ions.
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035 $a (UMI)AAI3292726
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100 1 $a Yaman, Gulsah. $3 1282255
245 1 0 $a Chemistry of a new trispyrazolylborate ligand with some group 1 group 2 ions.
300 $a 219 p.
500 $a Adviser: Malcolm H. Chisholm.
500 $a Source: Dissertation Abstracts International, Volume: 68-12, Section: B, page: 8027.
502 $a Thesis (Ph.D.)--The Ohio State University, 2008.
520 $a All of the compounds have been characterized by elemental analysis, NMR spectroscopy, and by single-crystal X-ray studies, the latter of which reveal the versatile modes of binding for this new ligand bearing hemilabile ether appendages.
520 $a Single-site metal alkoxide initiators with a general formula of LM-OR, where L is a bulky inert ligand, are currently used to catalyze the ring-opening polymerization (ROP) of lactides and other cyclic esters with good control. In this study, a new trispyrazolylborate ligand, Tp*, containing a 3-substituted pyrazole with --CMe2CH2OMe group has been synthesized. The Tp* ligand is a potentially hexadentate kappa6-N 3,O3-donor ligand. By synthesizing this new ligand we aimed that this ligand can form a pocket around Ca2+ in order to protect the metal center against ligand scrambling, transesterification, or deactivation by impurities, such as water.
520 $a First, the synthesis of 3-(2-methoxy-1,1-dimethylethyl)pyrazole, pz*H is described together with its reactions with the borohydrides MBH4, where M = Li, Na, and K, under melt conditions. At 180°C, this procedure leads to a mixture of products for M = Li, and at higher temperatures, a derivative LiTp'pz*H is isolated, wherein a B-H bond and a methyl group have been eliminated and a B-O bond has been formed. For M = Na, the reaction proceeds to give the tris-pyrazolylborate derivative NaTp* but at higher temperatures the tetra-pyrazolylborate complex NaB(pz*)4 is obtained. The reactions involving KBH 4 and pz*H yield the dinuclear complex K2(Tp*)2pz*H. The reaction between NaTp* and TlOAc in dichloromethane at room temperature leads to the formation of TlTp* along with NaOAc. Thallium(I) cation is an efficient ligand transfer agent for Tp* ligand. TlTp* reacts with methyllithium in diethylether to give LiTp* and thallium metal, and, similarly, TlTp* and KH react in THF to give KTp* and Tl(0). In addition, the heavier alkaline earth metal iodides (Tp*MI where M = Ca, Sr and Ba) were easily synthesized by using TlTp* and the corresponding metal diiodide, MI2, in THF. However, Tp*MgI and Tp*ZnI are obtained from the reaction of MI2 and NaTp* in THF and dichloromethane, respectively. In the solid state structures of the magnesium and calcium complexes there are no close contacts to the iodide and thus they exist as salts: [Tp*M]+I-. While strontium and barium complexes of the form Tp*M(I) have iodide bound to the metal with one other donor ligand such as THF. Natural bond orbital (NBO) analyses revealed that the metal ligand-bonding in pseudo-octahedral MTp* complexes is largely ionic.
520 $a The reaction between Ca[N(SiMe3)2]2(THF) 2 and TlTp* yields Tp*CaN(SiMe3)2 via [CaTp*] +{Ca[N(SiMe3)2]3}-. Heating Tp*CaN(SiMe3)2 gives CaTp*2 by disproportionation. Whereas MgTp*2 is prepared from MgBu2 and TlTp* in THF. Both CaTp*2 and MgTp*2 exist as salts in the solid state: [Tp*M]+[Tp*], but in solution the calcium compound undergoes dynamic Tp* exchange on the NMR time-scale. Slower ligand exchange in MgTp* 2 is studied by variable temperature 13C{1H}-NMR spin saturation transfer experiments.
520 $a The reaction between Tp*CaN(SiMe3)2 and p-cresol in benzene gives Tp*CaOC6H4-p-Me, a seven-coordinate calcium alkoxide. Tp*CaOC6H4-p-Me is a useful initiator for ROP of L-LA in benzene-d6 at room temperature, and it can sustain the polymerization with further stepwise loadings of L-LA. In addition, it is active for ROP of rac-LA, trimethylene carbonate (TMC) and epsilon-caprolactone (epsilon-CL) in benzene-d6.
590 $a School code: 0168.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Polymer. $3 1018428
690 $a 0488
690 $a 0495
710 2 $a The Ohio State University. $3 718944
773 0 $t Dissertation Abstracts International $g 68-12B.
790 $a 0168
790 1 0 $a Chisholm, Malcolm H., $e advisor
791 $a Ph.D.
792 $a 2008
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3292726