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Reactivity Studies of Bulky Terphenyl Ligand Supported Low Valent Tin(II) Hydride Species toward Unsaturated Olefins and the Synthesis and Reactivity Investigation of the Low Valent Tin(II) Azide.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Reactivity Studies of Bulky Terphenyl Ligand Supported Low Valent Tin(II) Hydride Species toward Unsaturated Olefins and the Synthesis and Reactivity Investigation of the Low Valent Tin(II) Azide./
作者:	Wang, Shuai.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2017,
面頁冊數:	186 p.
附註:	Source: Dissertations Abstracts International, Volume: 79-10, Section: B.
Contained By:	Dissertations Abstracts International79-10B.
標題:	Inorganic chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10639859
ISBN:	9780355763706

Reactivity Studies of Bulky Terphenyl Ligand Supported Low Valent Tin(II) Hydride Species toward Unsaturated Olefins and the Synthesis and Reactivity Investigation of the Low Valent Tin(II) Azide.
Wang, Shuai.

Reactivity Studies of Bulky Terphenyl Ligand Supported Low Valent Tin(II) Hydride Species toward Unsaturated Olefins and the Synthesis and Reactivity Investigation of the Low Valent Tin(II) Azide. - Ann Arbor : ProQuest Dissertations & Theses, 2017 - 186 p.

Source: Dissertations Abstracts International, Volume: 79-10, Section: B.

Thesis (Ph.D.)--University of California, Davis, 2017.

This item must not be sold to any third party vendors.

This dissertation describes investigation of the reactivity of terphenyl supported low valent tin(II) hydrides, [ArSn(μ-H)]2 (Ar = Ar iPr6 or AriPr4; AriPr6 = C6H 3-2,6(C6H2-2,4,6-iPr 3)2, AriPr4 = C6H3-2,6(C6 H3-2,6-iPr2) 2) toward both acyclic and bicyclic unsaturated olefins, and the synthesis, characterization, and reactivity studies of the first low valent doubly bridged tin(II) azides. The solid state structures of new compounds were determined by single crystal X-ray crystallography. Nuclear magnetic resonance spectroscopy, UV-Visible spectroscopy, infrared spectroscopy, and electron paramagnetic resonance spectroscopy were employed to characterize the compounds when applicable. The fast ligand site exchange rate between the ethyl and methyl substituted distannenes, (ArSnR)2 (R = Me or Et), and stannylstannylenes, ArSnSnR 2Ar; the equilibrium constant of the t-butylethyl group exchange between the distannenes, (ArSnCH2CH2tBu) 2 and stannylstannylenes, ArSnSn(CH2CH2 tBu)2Ar; and the rearrangement of the norbornenyl group of ArSn(norbornenyl) to the norticylyl group of ArSn(3-tricyclo[2.2.1.0 2,6]heptane) were all determined via VT 1H NMR experiments. Previous investigation of low valent group 14 hydrides are described in Chapter 1. In Chapter 2, the tin(II) hydride [AriPr6Sn(μ-H)] 2 (AriPr6 = C6H3-2,6(C6H 2-2,4,6-iPr3)2) (1a) is shown to react with two equivalents of ethylene or t-butylethylene under ambient conditions to yield the tetraorganoditin species Sn2AriPr62R2 (R = ethyl or t-butylethyl), which have two isomeric forms: a symmetric distannene [AriPr6SnR]2 (2a or 5a) or an unsymmetric stannylstannylene AriPr6SnSnR 2AriPr6 (3a), which, in solution, are in equilibrium with each other and also with the monomer :SnRAriPr6. In contrast, the slightly less crowded tin(II) hydride [AriPr4Sn(μ-H)] 2 (AriPr4 = C6H3-2,6(C6H 3-2,6-iPr2)2) (1b) reacts with excess ethylene to give AriPr4(CH 2CH3)2Sn(CH2CH2)Sn(CH 2CH3)(CHCH2)AriPr4 ( 4) in which five ethylene equivalents have been absorbed, one of which is dehydrogenated to an alkenyl, -CH=CH2, group. Nonetheless the AriPr4 isomers of 2a and 3a, ie. [AriPr4Sn(C2H5)]2 (2b) and AriPr4SnSn(C2H5) 2AriPr4 (3b) were obtained by reaction of [AriPr4Sn(μ-Cl)]2 with EtLi or EtMgBr. The isomeric pairs 2a/2b and 3a/3b are separated by crystallization at different temperatures. Variable temperature (VT) 1H NMR studies establish the existence of the fast ethyl group exchange between Ar(C 2H5)SnSn(C2H5)Ar (Ar = AriPr6 (2a) or AriPr4 (2b)) and ArSnSn(C2H5)2Ar (Ar = AriPr6 (3a) or AriPr4 (3b)) with ΔG‡ activation energies of 14.2±0.65 kcal mol-1 for 2a/3a and 14.8±0.36 kcal mol-1 for 2b/3b. The more crowded t-butylethyl substituted distannenes [ArSn(CH 2CH2tBu)]2 (Ar = AriPr6 (5a) or AriPr4 ( 5b)), which are obtained by reaction of 1a or 1b with t-butylethylene, dissociates to ArSnCH2CH2 tBu monomers in solution. At lower temperature they interconvert with their stannylstannylene isomers with the equilibrium parameters Keq = 4.09 ± 0.16 for 5a and and 6.38 ± 0.41 for 5b and Gibbs free energy ΔGeq = -1.81±0.19 kcal mol-1 for 5a, and -1.0±0.03 kcal mol-1 for 5b at 298 K. The 1:1 reaction of the hydrides 1a or 1b with the distannenes 5a or 5b yield the previously unknown monohydrido species of the general formula Sn2RHAr2 which were shown to have the structures AriPr6Sn-Sn(H)(CH2CH2 tBu)AriPr6 (6a), or the mono-hydrido bridged AriPr4Sn(μ-H)Sn(CH2CH2 tBu)AriPr4 (6b). The latter represents the first structural characterization of an isolated mono-hydrido bridged isomeric form of a ditetrelene. In Chapter 3, the reactions of the tin(II) hydrides, [ArSn(μ-H)]2 (1) (Ar = AriPr4 (1a) or Ar iPr6 (1b), AriP4 = C6H3-2,6-(C 6H3-2,6-iPr2) 2, AriPr6 = C6H3-2,6- (C6 H2-2,4,6-iPr3) 2) with norbornene (NB) or norbornadiene (NBD) readily generate the bicyclic alkyl/alkenyl substituted stannylenes, ArSn(norbornyl) (2a or 2b) or ArSn(norbornenyl) (3a or 3b), respectively. Heating a toluene solution of 3a or 3b at reflux afforded the rearranged species, ArSn(3-tricyclo[2.2.1.0 2,6]heptane) (4a or 4b), in which the norbornenyl ligand is transformed into a nortricyclyl group. 1H NMR Studies of the reactions of 4a or 4b with t-butylethylene indicated the existence of an apparently unique reversible β-hydride elimination from the bicyclic substituted aryl/alkyl stannylenes 2a or 2b and 3a or 3b. Mechanistic studies indicated that the transformation of 3a or 3b into 4a or 4b occurs via a β-hydride elimination of 1a or 1b to regenerate NBD. Kinetic studies showed that the conversion of 3a or 3b to 4a or 4b is first order with the rate constant k determined to be 3.33 · 10-5 min-1, with activation energy Ea of 95.9±4.4 kJ mol-1. In Chapter 4, a simple exchange reaction between [AriPr4Sn(μ-Cl)] 2 (1) and sodium azide afforded the doubly bridged tin(II) azide, [Ar iPr4Sn(μ-N3)]2 (2) (Ar iPr4 = C6H3-2,6(C6H3-2,6- iPr2)2) in 85 % yield. Exposure of a diethyl ether solution of 2 under UV light for ca. 16 h yielded an azepinyl substituted insertion product, [C 6H3-2-(C6H3-2,6-iPr 2)-6-(C6H3N-3,7- iPr 2)Sn]2 (3). The reaction of the Lewis acid, B(C6F5)3 (BCF), or the Lewis base, pyridine, with 2 leads the dissociation of the dimer to afford the corresponding coordinated monomeric tin(II) azide, AriPr4SnN3BCF (4), or AriPr4Sn(pyridine)N3 ( 6). Photolysis of 4 in diethyl ether for 12 h led to insertion of the α-nitrogen of the azide group to one of the B-C bonds of the BCF to yield the tin(II) amide, AriPr4SnN(C6F5)B(C6F 5)2 (5). In contrast photolysis of 6 for over 36 h afforded no reaction. A reactive Sn nitride intermediate, AriPr4 Sn=N, is proposed as part of the mechanistic pathway in the formation of 3 and 5.

ISBN: 9780355763706Subjects--Topical Terms:

3173556
Inorganic chemistry.
Subjects--Index Terms:

Group 14 metal

Reactivity Studies of Bulky Terphenyl Ligand Supported Low Valent Tin(II) Hydride Species toward Unsaturated Olefins and the Synthesis and Reactivity Investigation of the Low Valent Tin(II) Azide.
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100 1 $a Wang, Shuai. $3 3288111
245 1 0 $a Reactivity Studies of Bulky Terphenyl Ligand Supported Low Valent Tin(II) Hydride Species toward Unsaturated Olefins and the Synthesis and Reactivity Investigation of the Low Valent Tin(II) Azide.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2017
300 $a 186 p.
500 $a Source: Dissertations Abstracts International, Volume: 79-10, Section: B.
500 $a Publisher info.: Dissertation/Thesis.
500 $a Advisor: Power, Philip P.
502 $a Thesis (Ph.D.)--University of California, Davis, 2017.
506 $a This item must not be sold to any third party vendors.
520 $a This dissertation describes investigation of the reactivity of terphenyl supported low valent tin(II) hydrides, [ArSn(μ-H)]2 (Ar = Ar iPr6 or AriPr4; AriPr6 = C6H 3-2,6(C6H2-2,4,6-iPr 3)2, AriPr4 = C6H3-2,6(C6 H3-2,6-iPr2) 2) toward both acyclic and bicyclic unsaturated olefins, and the synthesis, characterization, and reactivity studies of the first low valent doubly bridged tin(II) azides. The solid state structures of new compounds were determined by single crystal X-ray crystallography. Nuclear magnetic resonance spectroscopy, UV-Visible spectroscopy, infrared spectroscopy, and electron paramagnetic resonance spectroscopy were employed to characterize the compounds when applicable. The fast ligand site exchange rate between the ethyl and methyl substituted distannenes, (ArSnR)2 (R = Me or Et), and stannylstannylenes, ArSnSnR 2Ar; the equilibrium constant of the t-butylethyl group exchange between the distannenes, (ArSnCH2CH2tBu) 2 and stannylstannylenes, ArSnSn(CH2CH2 tBu)2Ar; and the rearrangement of the norbornenyl group of ArSn(norbornenyl) to the norticylyl group of ArSn(3-tricyclo[2.2.1.0 2,6]heptane) were all determined via VT 1H NMR experiments. Previous investigation of low valent group 14 hydrides are described in Chapter 1. In Chapter 2, the tin(II) hydride [AriPr6Sn(μ-H)] 2 (AriPr6 = C6H3-2,6(C6H 2-2,4,6-iPr3)2) (1a) is shown to react with two equivalents of ethylene or t-butylethylene under ambient conditions to yield the tetraorganoditin species Sn2AriPr62R2 (R = ethyl or t-butylethyl), which have two isomeric forms: a symmetric distannene [AriPr6SnR]2 (2a or 5a) or an unsymmetric stannylstannylene AriPr6SnSnR 2AriPr6 (3a), which, in solution, are in equilibrium with each other and also with the monomer :SnRAriPr6. In contrast, the slightly less crowded tin(II) hydride [AriPr4Sn(μ-H)] 2 (AriPr4 = C6H3-2,6(C6H 3-2,6-iPr2)2) (1b) reacts with excess ethylene to give AriPr4(CH 2CH3)2Sn(CH2CH2)Sn(CH 2CH3)(CHCH2)AriPr4 ( 4) in which five ethylene equivalents have been absorbed, one of which is dehydrogenated to an alkenyl, -CH=CH2, group. Nonetheless the AriPr4 isomers of 2a and 3a, ie. [AriPr4Sn(C2H5)]2 (2b) and AriPr4SnSn(C2H5) 2AriPr4 (3b) were obtained by reaction of [AriPr4Sn(μ-Cl)]2 with EtLi or EtMgBr. The isomeric pairs 2a/2b and 3a/3b are separated by crystallization at different temperatures. Variable temperature (VT) 1H NMR studies establish the existence of the fast ethyl group exchange between Ar(C 2H5)SnSn(C2H5)Ar (Ar = AriPr6 (2a) or AriPr4 (2b)) and ArSnSn(C2H5)2Ar (Ar = AriPr6 (3a) or AriPr4 (3b)) with ΔG‡ activation energies of 14.2±0.65 kcal mol-1 for 2a/3a and 14.8±0.36 kcal mol-1 for 2b/3b. The more crowded t-butylethyl substituted distannenes [ArSn(CH 2CH2tBu)]2 (Ar = AriPr6 (5a) or AriPr4 ( 5b)), which are obtained by reaction of 1a or 1b with t-butylethylene, dissociates to ArSnCH2CH2 tBu monomers in solution. At lower temperature they interconvert with their stannylstannylene isomers with the equilibrium parameters Keq = 4.09 ± 0.16 for 5a and and 6.38 ± 0.41 for 5b and Gibbs free energy ΔGeq = -1.81±0.19 kcal mol-1 for 5a, and -1.0±0.03 kcal mol-1 for 5b at 298 K. The 1:1 reaction of the hydrides 1a or 1b with the distannenes 5a or 5b yield the previously unknown monohydrido species of the general formula Sn2RHAr2 which were shown to have the structures AriPr6Sn-Sn(H)(CH2CH2 tBu)AriPr6 (6a), or the mono-hydrido bridged AriPr4Sn(μ-H)Sn(CH2CH2 tBu)AriPr4 (6b). The latter represents the first structural characterization of an isolated mono-hydrido bridged isomeric form of a ditetrelene. In Chapter 3, the reactions of the tin(II) hydrides, [ArSn(μ-H)]2 (1) (Ar = AriPr4 (1a) or Ar iPr6 (1b), AriP4 = C6H3-2,6-(C 6H3-2,6-iPr2) 2, AriPr6 = C6H3-2,6- (C6 H2-2,4,6-iPr3) 2) with norbornene (NB) or norbornadiene (NBD) readily generate the bicyclic alkyl/alkenyl substituted stannylenes, ArSn(norbornyl) (2a or 2b) or ArSn(norbornenyl) (3a or 3b), respectively. Heating a toluene solution of 3a or 3b at reflux afforded the rearranged species, ArSn(3-tricyclo[2.2.1.0 2,6]heptane) (4a or 4b), in which the norbornenyl ligand is transformed into a nortricyclyl group. 1H NMR Studies of the reactions of 4a or 4b with t-butylethylene indicated the existence of an apparently unique reversible β-hydride elimination from the bicyclic substituted aryl/alkyl stannylenes 2a or 2b and 3a or 3b. Mechanistic studies indicated that the transformation of 3a or 3b into 4a or 4b occurs via a β-hydride elimination of 1a or 1b to regenerate NBD. Kinetic studies showed that the conversion of 3a or 3b to 4a or 4b is first order with the rate constant k determined to be 3.33 · 10-5 min-1, with activation energy Ea of 95.9±4.4 kJ mol-1. In Chapter 4, a simple exchange reaction between [AriPr4Sn(μ-Cl)] 2 (1) and sodium azide afforded the doubly bridged tin(II) azide, [Ar iPr4Sn(μ-N3)]2 (2) (Ar iPr4 = C6H3-2,6(C6H3-2,6- iPr2)2) in 85 % yield. Exposure of a diethyl ether solution of 2 under UV light for ca. 16 h yielded an azepinyl substituted insertion product, [C 6H3-2-(C6H3-2,6-iPr 2)-6-(C6H3N-3,7- iPr 2)Sn]2 (3). The reaction of the Lewis acid, B(C6F5)3 (BCF), or the Lewis base, pyridine, with 2 leads the dissociation of the dimer to afford the corresponding coordinated monomeric tin(II) azide, AriPr4SnN3BCF (4), or AriPr4Sn(pyridine)N3 ( 6). Photolysis of 4 in diethyl ether for 12 h led to insertion of the α-nitrogen of the azide group to one of the B-C bonds of the BCF to yield the tin(II) amide, AriPr4SnN(C6F5)B(C6F 5)2 (5). In contrast photolysis of 6 for over 36 h afforded no reaction. A reactive Sn nitride intermediate, AriPr4 Sn=N, is proposed as part of the mechanistic pathway in the formation of 3 and 5.
590 $a School code: 0029.
650 4 $a Inorganic chemistry. $3 3173556
653 $a Group 14 metal
653 $a Hydrostannylation
653 $a Organometallic
653 $a Terphenyl
653 $a Tin(ii) azide
690 $a 0488
710 2 $a University of California, Davis. $b Chemistry. $3 1679244
773 0 $t Dissertations Abstracts International $g 79-10B.
790 $a 0029
791 $a Ph.D.
792 $a 2017
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10639859