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Synthesis and reactivity study of low-valent group 14 metal compounds supported by pyridyl-1-azaallyl and iminophosphoranyl ligands. / CUHK electronic theses & dissertations collection

本論文工作主要包括三部分: (i) 含吡啶基-1-氮雜烯丙基配體的二价鍺氯化物的反應研究; (ii) 含吡啶基-1-氮雜烯丙基配體的一价鍺二聚體的合成及反應研究; (iii) 膦亞胺配體衍生的低价態第十四族金屬復合物及金屬亞乙烯的合成與反應研究。 / 第一章描述含吡啶基-1-氮雜烯丙基配位體的二价鍺氯化物66的反應。化合物66與Na[M(η⁵-C₅H₅)(CO)₃]2DME (M = Mo or W)反應,得到含鍺(II)-金屬單鍵的異核雙金屬鍺亞乙烯化合物76及77。化合物66與環戊二烯鈉反應生成了環戊二烯基取代的鍺烯。作為路易斯鹼,化合物66與大位阻硼烷的反應得到研究。化合物66與B(C₆F₅)₃反應,得到路易斯酸-鹼加合物79。此外,化合物66與三价氯化鎵及三价氯化銦進行的配體轉移反應也得到研究。另外,化合物66與水的反應產生[{HNC(Ph)CH(C₅H₄N-2)}GeCl] (82)。 / 第二章描述化合物66的還原化學。二价鍺氯化物66與過量鎂反應得到 [N(SiMe₃)C(Ph)C(SiMe₃) (C₅H₄N-2)Mg(μ-Cl)(THF)]₂ (110)和[C(Ph)C(SiMe₃)(C₅H₄N-2)]₂Ge₂ (111)的混合物。而其與過量金屬鋰反應則得到一价鍺二聚體[C(Ph)C(SiMe₃)(C₅H₄N-2)]₂Ge₂ (111)及[N(SiMe₃)C(Ph)C(SiMe₃) (C₅H₄N-2)]₂Ge₂ (112)。化合物66與等當量石墨鉀反應,主要得到一价鍺二聚體112。化合物112與偶氮苯反應得到鍺聯氨衍生物[PhNGe{N(SiMe₃) C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂₋(113)。化合物112的路易斯鹼性得到研究。化合物112與一當量九羰基二鐵反應生成新型不對稱一价鍺二聚體[{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}](114),而其與兩當量九羰基二鐵反應則得到[{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)Fe(CO)₄)Ge]₂(115)。此外,二聚體112與硫磺進行反應,得到首個鍺二硫代羧酸酐的鍺類似物。 / 第三章介紹從膦亞胺配體衍生的二价態第十四族金屬復合物的合成,描述了由配體Ph₂P(2-CH₂Py)=NSiMe₃ (119)及H₂C(PPh₂=NSiMe₃)₂ (121)衍生的二价鍺及二价錫化合物的合成。此外,本章研究了半穏定配體Ph₂PCH₂(PPh₂=NSiMe₃) (131)的配位化學。化合物131在Bu[superscript n]Li及Bu[superscript n]₂Mg的作用下金屬化分解反應,分別生成膦亞胺鋰化合物[Li{CH(PPh₂)(PPh₂=NSiMe₃)}(THF)₂] (194)及鎂化合物[Mg{CH(PPh₂)(PPh₂=NSiMe₃)}₂] (193)。化合物194與相應的二价金屬氯化物反應得到1,3-二錫環丁烷196和1,3-二鉛環丁烷200。化合物194與二氯化鍺二噁烷配合物的反應得到新型三核雜環化合物195。此外,化合物196與九羰基二鐵反應,得到膦穏定的錫亞乙烯197。 / 第四章為第一至第三章的總結。 / This thesis is focused on three areas: (i) the reactivities of pyridyl-1-azaallyl germanium(II) chloride; (ii) the synthesis and reactivities of pyridyl-1-azaallyl germanium(I) dimer; (iii) the synthesis and reactivities of low-valent main group 14 metal complexes and metallavinylidenes derived from phosphoranoimines. / Chapter 1 describes the reactivities of pyridyl-1-azaallyl germanium(II) chloride [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}GeCl] (66). The reaction of 66 with Na[M(η⁵-C₅H₅)(CO)₃]2DME (M = Mo or W) affords heterobimetallic germylenes 76 and 77 which contain a germanium(II)-metal single bond. A Cp-substituted germylene was prepared from the reaction of 66 with sodium cyclopentadienylide. The Lewis base behavior of 66 toward bulky borane was investigated. Treatment of 66 with B(C₆F₅)₃ leads to the formation of a Lewis acid-base adduct 79. Furthermore, the ligand transfer reaction of 66 with GaCl₃ and InCl₃ were studied. In addition, the reaction of 66 with water affords [{HNC(Ph)CH(C₅H₄N-2)}GeCl] (82). / Chapter 2 describes the reduction chemistry of 66. Treatment of 66 with excess magnesium tunings affords a mixture of products [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)Mg(μ-Cl)(THF)]₂ (110) and [C(Ph)C(SiMe₃)(C₅H₄N-2)]₂Ge₂ (111). The reaction of 66 with an excess of lithium metals leads to a mixture of germanium(I) dimers [C(Ph)C(SiMe₃)(C₅H₄N-2)]₂Ge₂ (111) and [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (112). When compound 66 was treated with one equivalent of potassium graphite, compound 112 was obtained as the major product. The reaction of 112 with azobenzene affords the 1,2-digermylene hydrazinide [PhNGe{N(SiMe₃) C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂ (113). The Lewis base behaviour of 112 was studied. Treatment of 112 with one equivalent of diironnonacarbonyl gives a new unsymmetric germanium(I) dimer [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}] (114), while the reaction of 112 with two equivalent of diironnonacarbonyl leads to the formation of [{N(SiMe₃)C- (Ph)C(SiMe₃)(C₅H₄N-2)Fe(CO)₄)Ge]₂ (115). In addition, the reaction of 112 with sulfur affords the first germanium analogue of a dithiocarboxylic acid anhydride. / Chapter 3 deals with the synthesis of group 14 metal(II) complexes supported by iminophosphoranyl ligands. The synthesis of germanium(II) and tin(II) compounds derived from Ph₂P(2-CH₂Py)=NSiMe₃ (119) and H₂C(PPh₂=NSiMe₃)₂ (121) are described. Furthermore, the coordination chemistry of the hemilabile ligand Ph₂PCH₂(PPh₂=NSiMe₃) (131) was investigated. Iminophosphoranyl phosphine 131 undergoes metalation with Bu[superscript n]Li and Bu[superscript n]₂Mg to give the lithium complex [Li{CH(PPh₂)(PPh₂=NSiMe₃)}(THF)₂] (194) and the magnesium complex [Mg{CH- (PPh₂)(PPh₂=NSiMe₃)}₂] (193), respectively. 1,3-distannylcyclobutane 196 and 1,3-diplumbacyclobutane 200 were prepared from the reaction of 194 with the corresponding metal(II) chlorides. The reaction of 194 with GeCl₂(dioxane) leads to a tri-nuclear heterocyclic cage compound 195. In addition, the trapping reaction of 196 with diironnonacarbonyl affords the phoshpine-stabilized stannavinylidene 197. / Chapter 4 describes the conclusion of the first three chapters. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Chiu, Wang Kin. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2013. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in also in Chinese. / Tables of Contents --- p.vi / Acknowledgments --- p.i / Abstract --- p.ii / 摘要 --- p.iv / List of Compounds Synthesized --- p.xiv / Abbreviations --- p.xvi / Chapter Chapter 1 --- Reactivity of Pyridyl-1-azaallyl Germanium(II) Chloride / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- Reactivity Study of Heteroleptic Organogermanium(II) Chlorides --- p.1 / Chapter 1.1.2 --- Synthesis and Structure of Pyridyl-1-azaallyl Germanium(II) Chloride --- p.13 / Chapter 1.1.3 --- Objectives --- p.15 / Chapter 1.2 --- Results and Discussion --- p.18 / Chapter 1.2.1.1 --- Synthesis of Metallo-germylenes from Pyridy1-1-azaallyl Germanium (II) chloride --- p.19 / Chapter 1.2.1.2 --- Spectroscopic Properties of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}Ge-M(η⁵-C₅H₅)(CO)₃] (M = Mo (76), W (77) --- p.19 / Chapter 1.2.1.3 --- Molecular Structures of [{N(SiMe₃)C(Ph)C(SiMe₃) (C₅H₄N-2)}Ge-M(η⁵-C₅H₅)(CO)₃] (M = Mo (76), W (77)) --- p.20 / Chapter 1.2.2.1 --- Synthesis of Heteroleptic Germylene [{N(SiMe₃)C(Ph)C- (SiMe₃)(C₅H₄N-2)}Ge(η¹-C₅H₅)] (78) --- p.25 / Chapter 1.2.2.2 --- Spectroscopic Properties of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}Geη¹-C₅H₅)] (78) --- p.25 / Chapter 1.2.2.3 --- Molecular Structures of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}Ge(η¹-C₅H₅)] (78) --- p.26 / Chapter 1.2.3.1 --- Synthesis of Germanium(II)-Borane Adduct Adduct Adduct [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}Ge(Cl)→(B(C₆H₅)₃)] (79) --- p.29 / Chapter 1.2.3.2 --- Spectroscopic Properties of Germanium(II)-Borane Adduct Adduct [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}Ge(Cl)→(B(C₆H₅)₃)](79) --- p.29 / Chapter 1.2.3.3 --- Molecular Structures of Germanium(II)-Borane Adduct Adduct [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}Ge(Cl)→(B(C₆H₅)₃)](79) --- p.30 / Chapter 1.2.4.1 --- Synthesis of Pyridyl-1-azaallyl Group 13 Metal Complexes from the Ligand Transfer Reaction between Pyridyl-1-azaallyl Germanium(II) Chloride and Group 13 Metal Halides --- p.34 / Chapter 1.2.4.2 --- Spectroscopic Properties of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}GaCl₂] (80) and [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}₂InCl] (81) --- p.35 / Chapter 1.2.4.3 --- Molecular Structures of [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}GaCl₂] (80) and [{N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)}₂InCl] (81) --- p.36 / Chapter 1.2.5.1 --- Hydrolysis of Pyridyl-1-azaallyl Germanium(II) Chloride with Water --- p.40 / Chapter 1.2.5.2 --- Spectroscopic Properties of [{HNC(Ph)CH(C₅H₄N-2)}GeCl] (82) --- p.40 / Chapter 1.2.5.3 --- Molecular Structure of [{HNC(Ph)CH(C₅H₄N-2)}GeCl] (82) --- p.41 / Chapter 1.3 --- Experimental for Chapter 1 --- p.43 / Chapter 1.4 --- References for Chapter 1 --- p.49 / Chapter Chapter 2 --- Synthesis and Reactivity Study of Pyridyl-1-azaallyl Germanium(I) Dimer / Chapter 2.1 --- Introduction --- p.55 / Chapter 2.1.1 --- General Aspects of Digermynes and Germanium(I) Dimers Supported by Bulky Ligands --- p.55 / Chapter 2.1.2 --- Objectives --- p.67 / Chapter 2.2 --- Results and Discussion --- p.69 / Chapter 2.2.1.1 --- Reduction of Pyridyl-1-azaallyl Germanium(II) Chloride:Synthesis of Germanium(I) Dimers [C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (111) and [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (112) --- p.69 / Chapter 2.2.1.2 --- Spectroscopic Properties of [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)Mg(μ-Cl)(THF)]₂ (110), [C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (111) and [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (112) --- p.71 / Chapter 2.2.1.3 --- Molecular Structures of [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)Mg(μ-Cl)(THF)]₂(110), [C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (111) and [N(SiMe₃)C(Ph)C(SiMe₃)- (C₅H₄N-2)]₂Ge₂ (112) --- p.72 / Chapter 2.2.2.1 --- Synthesis of [PhNGe{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂ (113) --- p.80 / Chapter 2.2.2.2 --- Spectroscopic Properties of [PhNGe{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂ (113) --- p.80 / Chapter 2.2.2.3 --- Molecular Structure of [PhNGe{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂ (113) --- p.80 / Chapter 2.2.3.1 --- Synthesis of [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)4)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}] (114) and [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)4)Ge]₂ (115) --- p.84 / Chapter 2.2.3.2 --- Spectroscopic Properties of [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}](114) and [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)Ge]₂ (115) --- p.86 / Chapter 2.2.3.3 --- Molecular Structures of [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)- Ge-Ge{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}](114) and [{N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)(Fe(CO)₄)Ge]₂ (115) --- p.87 / Chapter 2.2.4.1 --- Synthesis of the First Germanium Analogue of a Dithiocarboxylic Acid Anhydride: [Ge(S){N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂S (117) --- p.90 / Chapter 2.2.4.2 --- Spectroscopic Properties of [Ge(S){N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂S (117) --- p.91 / Chapter 2.2.4.3 --- Molecular Structure of [Ge(S){N(SiMe₃)C(Ph)C(SiMe₃)(C₅H₄N-2)}]₂S (117) --- p.92 / Chapter 2.3 --- Experimental for Chapter 2 --- p.95 / Chapter 2.4 --- References for Chapter 2 --- p.103 / Chapter Chapter 3 --- Synthesis and Characterization of Iminophosphoranyl Methanide Metal Complexes and Group 14 Metallavinylidenes / Chapter 3.1 --- Introduction --- p.109 / Chapter 3.1.1 --- A General Review of Phosphoranoimine Ligands --- p.109 / Chapter 3.1.2 --- A General Review of Group 14 Metal Complexes Containing Phosphoranoimine Ligands --- p.117 / Chapter 3.1.3 --- Objectives --- p.124 / Chapter 3.2 --- Results and Discussion --- p.126 / Chapter 3.2.1.1 --- Synthesis of Heteroleptic Chlorogermylene [{(C₅H₄N-2)C(SiMe₃)P(Ph)₂N(SiMe₃)}GeCl (189) and Chlorostannylene [{(C₅H₄N-2)C (SiMe₃)P(Ph)₂N(SiMe₃)}SnCl] (190) --- p.126 / Chapter 3.2.1.2 --- Spectroscopic Properties of [{(C₅H₄N-2)C(SiMe₃)P(Ph)₂N(SiMe₃)}GeCl (189) and Chlorostannylene [{(C₅H₄N-2)C (SiMe₃)P(Ph)₂N(SiMe₃)}SnCl] (190) --- p.127 / Chapter 3.2.1.3 --- Molecular Structures of [{(C₅H₄N-2)C(SiMe₃)P(Ph)₂N(SiMe₃)}GeCl (189) and Chlorostannylene [{(C₅H₄N-2)C (SiMe₃)P(Ph)₂N(SiMe₃)}SnCl] (190) --- p.128 / Chapter 3.2.2.1 --- Synthesis of Bis(iminophosphoranyl) Germanium(II) Compounds [{H₂C(PPh₂=NSiMe₃)₂}(GeCl₂)] (191) and [HC(PPh₂=N- SiMe₃)₂Ge(η¹-C₅H₅)] (192) --- p.132 / Chapter 3.2.2.2 --- Spectroscopic Properties of [{H₂C(PPh₂=NSiMe₃)₂}(GeCl₂)] (191) and [HC(PPh₂=NSiMe₃)₂Ge(η¹-C₅H₅)] (192) --- p.133 / Chapter 3.2.2.3 --- Molecular Structures of [{H₂C(PPh₂=NSiMe₃)₂}(GeCl₂)] (191) and [HC(PPh₂=NSiMe₃)₂Ge(η¹-C₅H₅)] (192) --- p.134 / Chapter 3.2.3.1 --- Synthesis of Magnesium and Lithium Methanide Complexes [Mg{CH(PPh₂)(PPh₂=NSiMe₃)}₂] (193) and [Li{CH(PPh₂)- (PPh₂=NSiMe₃)}(THF)₂] (194) --- p.139 / Chapter 3.2.3.2 --- Spectroscopic Properties of [Mg{CH(PPh₂)(PPh₂=NSiMe₃)}₂] (193) and [Li{CH(PPh₂)- (PPh₂=NSiMe₃)}(THF)₂] (194) --- p.140 / Chapter 3.2.3.3 --- Molecular Structures of [Mg{CH(PPh₂)(PPh₂=NSiMe₃)}₂] (193)and [Li{CH(PPh₂)- (PPh₂=NSiMe₃)}(THF)₂] (194) --- p.141 / Chapter 3.2.4.1 --- Synthesis of Phosphine-Stabilized Germavinylidene [{(PPh₂=NSiMe₃)(PPh₂)C=Ge:}{(PPh₂=NSiMe₃)(PPh₂)C}₂Ge→Ge:] (195) --- p.145 / Chapter 3.2.4.2 --- Spectroscopic Properties of [{(PPh₂=NSiMe₃)(PPh₂)C=Ge:}{(PPh₂=NSiMe₃)(PPh₂)C}₂Ge→Ge:] (195) --- p.146 / Chapter 3.2.4.3 --- Molecular Structure of [{(PPh₂=NSiMe₃)(PPh₂)C=Ge:}{(PPh₂=NSiMe₃)(PPh₂)C}₂Ge→Ge:] (195) --- p.146 / Chapter 3.2.5.1 --- Synthesis of Phosphine-Stabilized Stannavinylidene [{(PPh₂=NSiMe₃)(PPh₂)C=Sn:}{(PPh₂=NSiMe₃)(PPh₂)C=Sn→ Fe(CO)₄}] (197) --- p.151 / Chapter 3.2.5.2 --- Spectroscopic Properties of [Sn{{471}²-C(PPh₂=NSiMe₃)(PPh₂)}](196) and [{(PPh₂=NSiMe₃)(PPh₂)C=Sn:}{(PPh₂=NSiMe₃)(PPh₂)C=Sn→Fe(CO)₄}] (197) --- p.152 / Chapter 3.2.5.3 --- Molecular Structures of [Sn{{471}²-C(PPh₂=NSiMe₃)(PPh₂)}] (196) and [{(PPh₂=NSiMe₃)(PPh₂)C=Sn:}{(PPh₂=NSiMe₃)(PPh₂)C=Sn→Fe(CO)₄}] (197) --- p.157 / Chapter 3.2.6.1 --- Synthesis of 1, 3-diplumbacyclobutane [Pb{{471}²-C(PPh₂=NSiMe₃)- (PPh₂)}]₂ (200) derived from iminophosphoranyl phosphine --- p.163 / Chapter 3.2.6.2 --- Spectroscopic Properties of [Pb{{471}²-C(PPh₂=NSiMe₃)- (PPh₂)}]₂ (200) --- p.164 / Chapter 3.2.6.3 --- Molecular Structure of [Pb{{471}²-C(PPh₂=NSiMe₃)- (PPh₂)}]₂ (200) --- p.164 / Chapter 3.3 --- Experimental for Chapter 3 --- p.167 / Chapter 3.4 --- References for Chapter 3 --- p.176 / Chapter Chapter 4 --- Conclusion / Chapter 4.1 --- Conclusion --- p.186 / Chapter 4.1.1 --- Reactivity Study of Pyridyl-1-azaallyl Germanium(II) Chloride --- p.186 / Chapter 4.1.2 --- Synthesis and Reactivity Study of Pyridyl-1-azaallyl Germanium(I) Dimer --- p.187 / Chapter 4.1.3 --- Synthesis and Characterization of Iminophosphoranyl Methanide Metal Complexes and Group 14 Metallavinylidenes --- p.191 / Chapter 4.2 --- References for Chapter 4 --- p.193 / Chapter Appendix I / Chapter A. --- General Procedures --- p.194 / Chapter B. --- Physical and Analytical Measurements --- p.194 / Chapter Appendix II / Chapter Table A.1. --- Selected Crystallographic Data for Compounds 76-79 --- p.197 / Chapter Table A.2. --- Selected Crystallographic Data for Compounds 80-82 and 110 --- p.198 / Chapter Table A.3. --- Selected Crystallographic Data for Compounds 111-114 --- p.199 / Chapter Table A.4. --- Selected Crystallographic Data for Compounds 117 and 118-191 --- p.200 / Chapter Table A.5. --- Selected Crystallographic Data for Compounds 192-195 --- p.201 / Chapter Table A.6. --- Selected Crystallographic Data for Compounds 196-197 and 200 --- p.202

Identiferoai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_328021
Date January 2013
ContributorsChiu, Wang Kin., Chinese University of Hong Kong Graduate School. Division of Chemistry.
Source SetsThe Chinese University of Hong Kong
LanguageEnglish, Chinese
Detected LanguageEnglish
TypeText, bibliography
Formatelectronic resource, electronic resource, remote, 1 online resource (xvii, 202 leaves) : ill.
RightsUse of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/)

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