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Synthesis and isolation of reactive ...

Zhang, Yun.

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Synthesis and isolation of reactive cations with weakly coordinating carborane anions.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Synthesis and isolation of reactive cations with weakly coordinating carborane anions./
Author:	Zhang, Yun.
Description:	243 p.
Notes:	Adviser: Christopher A. Reed.
Contained By:	Dissertation Abstracts International69-03B.
Subject:	Chemistry, Inorganic. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3305675
ISBN:	9780549523994

Synthesis and isolation of reactive cations with weakly coordinating carborane anions.
Zhang, Yun.

Synthesis and isolation of reactive cations with weakly coordinating carborane anions. - 243 p.

Adviser: Christopher A. Reed.

Thesis (Ph.D.)--University of California, Riverside, 2008.

Finally, attempts to synthesize a hypervalent hexacoordinate carbon compound are described in Chapter 8. Dimethylated S-allene has been isolated as a carborane salt. X-ray crystal data of this compound is described along with theoretical analysis.

ISBN: 9780549523994Subjects--Topical Terms:

517253
Chemistry, Inorganic.

Synthesis and isolation of reactive cations with weakly coordinating carborane anions.
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020 $a 9780549523994
035 $a (UMI)AAI3305675
035 $a AAI3305675
040 $a UMI $c UMI
100 1 $a Zhang, Yun. $3 1280801
245 1 0 $a Synthesis and isolation of reactive cations with weakly coordinating carborane anions.
300 $a 243 p.
500 $a Adviser: Christopher A. Reed.
500 $a Source: Dissertation Abstracts International, Volume: 69-03, Section: B, page: 1646.
502 $a Thesis (Ph.D.)--University of California, Riverside, 2008.
520 $a Finally, attempts to synthesize a hypervalent hexacoordinate carbon compound are described in Chapter 8. Dimethylated S-allene has been isolated as a carborane salt. X-ray crystal data of this compound is described along with theoretical analysis.
520 $a Carborane anions CHB11R5X6- (R = H, Me, X) (X = Cl, Br) are a class of weakly coordinating anions. They are weakly basic, extremely inert, non-nucleophilic, and nonoxidizing. Their interactions with cations are minimal, allowing the isolation of salts of highly reactive, highly acidic, and coordinatively unsaturated cations.
520 $a Cationic electrophiles paired up with carborane anions can achieve superelectrophilic activities. Thus, H(CHB11Cl11) is the strongest isolable Bronsted acid; Mc(CH11Me5Br6), sometimes referred to as "mighty methyl," is a much stronger Methylating agent than MeOTf; and R3Si(CH11Cl11) retains most of its R3Si+ character. These electrophiles can be used as reagents to explore the chemistry of weakly basic compounds. There are five different projects described in this dissertation. They are distributed into eight chapters. The following are the general descriptions of these five projects.
520 $a Chapters 2, 3, and 4 involve chemistries and applications of phosphazenes and polyphosphazenes. The weakly basic phosphazene, N3P3Cl 6, has been protonated, methylated, and silylated for isolation as carborane salts. Both protonated and methylated phosphazene could trigger ring-opening polymerization (ROP) of cyclic chlorophosphazene at 180°C in ODCB. Silylated phosphazene, on the other hand, could trigger ROP at room temperature and completed the ROP reaction in as little as 90 minutes. This is the first example of room temperature ROP of phosphazene. Both reaction mechanism and systematic studies are described.
520 $a Phosphininium ions are though to be transition states leading to lambda 5-phosphinines. To date, there is no example of electrophilic addition on lambda3-phosphinine due to its weakly basic nature. Chapter 5 describes the protonation and methylation reactions of lambda3 -phosphinine. Both NMR spectroscopic data and X-ray crystallography data are presented.
520 $a Tetra-methylhydrazine is a compound with two nitrogen atoms neighboring to each other. The challenge is to see if a dication can be made before breaking the N-N bond. Both di-protonated and di-methylated tetra-methylhydrazine are described in Chapter 6.
520 $a The 2-norbomyl cation has been studied in great detail by many investigators. The controversy is about whether the 2-norbomyl cation has a symmetrically bridged non-classical structure or is just a pair of classical trivalent ions in rapid equilibrium. Chapter 7 describes the synthesis and characterization of 2-norbomyl cation as a carborane salt. Its X-ray crystallography data is presented in this chapter.
590 $a School code: 0032.
650 4 $a Chemistry, Inorganic. $3 517253
650 4 $a Chemistry, Polymer. $3 1018428
690 $a 0488
690 $a 0495
710 2 $a University of California, Riverside. $3 791122
773 0 $t Dissertation Abstracts International $g 69-03B.
790 $a 0032
790 1 0 $a Reed, Christopher A., $e advisor
791 $a Ph.D.
792 $a 2008
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3305675