{"_buckets": {"deposit": "d02a84e4-bee6-4e71-bade-263a296d54cf"}, "_deposit": {"created_by": 1, "id": "160", "owners": [1], "pid": {"revision_id": 0, "type": "depid", "value": "160"}, "status": "published"}, "_oai": {"id": "oai:ir.soken.ac.jp:00000160", "sets": ["9"]}, "author_link": ["7677", "7678", "7679"], "item_1_biblio_info_21": {"attribute_name": "書誌情報（ソート用）", "attribute_value_mlt": [{"bibliographicIssueDates": {"bibliographicIssueDate": "1996-03-21", "bibliographicIssueDateType": "Issued"}, "bibliographic_titles": [{}]}]}, "item_1_creator_2": {"attribute_name": "著者名", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "小江, 誠司"}], "nameIdentifiers": [{"nameIdentifier": "7677", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_creator_3": {"attribute_name": "フリガナ", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "オゴウ, セイジ"}], "nameIdentifiers": [{"nameIdentifier": "7678", "nameIdentifierScheme": "WEKO"}]}]}, "item_1_date_granted_11": {"attribute_name": "学位授与年月日", "attribute_value_mlt": [{"subitem_dategranted": "1996-03-21"}]}, "item_1_degree_grantor_5": {"attribute_name": "学位授与機関", "attribute_value_mlt": [{"subitem_degreegrantor": [{"subitem_degreegrantor_name": "総合研究大学院大学"}]}]}, "item_1_degree_name_6": {"attribute_name": "学位名", "attribute_value_mlt": [{"subitem_degreename": "博士（理学）"}]}, "item_1_description_1": {"attribute_name": "ID", "attribute_value_mlt": [{"subitem_description": "1996020", "subitem_description_type": "Other"}]}, "item_1_description_12": {"attribute_name": "要旨", "attribute_value_mlt": [{"subitem_description": "  The purposes of this thesis are to develop a systematically synthetic method of higher-nuclearity heterometallic sulfide clusters, to investigate interactions of M-S-M\u0027 (M and M\u0027 = Rh, W, or Cu) groups in the newly prepared clusters, and to find an interesting reactivity of the M-S-M\u0027 groups in the clusters toward small molecules (e.g. H20 and H2S) from view points of a basic cluster chemistry.\n  Most clusters prepared in this research have been obtained by a unique building　block method as a rationally synthetic approach in which an organorhodium group (Cp*RhP(OEt)3, Cp* = η5 -C5 Me5) plays an important role to prevent from polymerizing of the products and to construct the higher-nuclearity heterometallic sulfide clusters soluble in common organic solvents.\n  In Chapter 1 the building-block approach toward a stepwise synthesis, [Cp*RhP(OEt)3 Cl2] (1) → [Cp*RhP(OEt)3 WS4] (2) → [Cp*RhP(OEt)3 (μ-WS4 )CuCl] (3) → [{Cp*RhP(OEt)3(μ-WS4)(CuCl)Cu}2(μ-Cl)2] (4), and as well as 1 → [{Cp*RhP(OEt)3}2 (μ-WS4)][BPh4]2 (5-[BPh4]2), is demonstrated.  The structures　of 1, 2, 3, 4, and 5-[BPh4]2 were confirmed by X-ray diffraction analysis.  The formation and structures of 3 and 4 have the following characteristics: the trinuclear sulfide cluster 3 possesses a linear sequence of Rh, W, and Cu atoms with octahedral, tetrahedral, and trigonal planar coordination geometries, respectively.  Although there　are three presumed geometrical isomers for 3 based on the difference in the binding site of CuCl on the WS4 core, the reaction between 2 and CuCl gave specifically 3 in nearly quantitative yield because the specific formation of 3 is due to the strong coordination ability of the terminal S atoms in 2 (see Scheme 1).  The linear-type framework of 3 is preserved in dichloromethane and acetonitrile solutions.\n As shown in Scheme 1 cluster 4 has an octanuclear framework with a crystallographic inversion center, and the eight metal atoms are arranged in a branched  configuration in which Rh…W…Cu1 is almost linear (172.43ﾟ) and Rh…W…Cu2 is an approximately right angle (90.73ﾟ).  The X-ray results indicate that cluster 3 performs a regiospecific CuCl-addition at S1 (or S1*) and S2 atoms to form 4.  This regiospecific addition is attributed mainly to a steric demand of the Cp* and P(OEt)3 ligands.  In dichloromethane cluster 4 exists as a tetranuclear species, [{Cp*RhP(0Et)3 (μ-WS4)(CuCl)2], however, in acetonitrile exists as 3 and the freed CuCl.\n  In Chapter 2 a unique conversion of a bridging S atom of 4 to a terminal 0 atom of [Cp*RhP(0Et)3 (μ-WOS3)(CuCl)Cu}2 (μ-Cl)2] (8) by the water saturated in dichloromethane is described.  This is the first example of the conversion of the bridging S atom in the M-S-M\u0027 groups into the terminal O atom without releasing the metal atoms.  The use of the water saturated in dichloromethane is essential, because the several attempts to obtain 8 from 4 by using aqueous acetonitrile, basic conditions in common solvents, and two-phase conditions of water and dichloromethane which gave 1, 3, [Cp*RhP(0Et)3 (μ-WOS3)(CuCl)] (7), and other unidentified products were not successful.  On the other hand, clusters 2 and 3 are little reacted with the water saturated in dichloromethane or water under two-phase conditions of water and dichloromethane in contrast to 4.  It seems that the specific reactivity of the W-S-Cu groups of 4 is dependent on differences in electron densities of the S atoms and steric effects of the Cp* and P (OEt)3 groups.  A tentative mechanism of the transformation reaction, 4 → 8, can be assumed as follows: water molecule interacts with the W atom and the S atom that has the high electron density in the four S atoms of the μ-WS4 group of 4 to give an intermediary species that has W-0-H and Cu-S-H groups, and then the species is transformed to 8.\n  Cluster 8 was also obtained by a stepwise synthesis using [WOS3]2- as a tungsten source:  1 → [Cp*RhP(OEt)3 (μ-S)2 W0S] (6a) → 7 → 8.  Cluster 6a is one of two possible geometrical isomers of [Cp*RhP(OEt)3 (μ-S)2 W0S].  The structures of 7 and 8 were determined by X-ray analysis.  In addition the reactions of 4, 7, and 8 with hydrogen sulfide to give 3 as the only major product are studied in Chapter 2.\n  In Chapter 3 it was investigated whether fast atom bombardment mass spectrometry (FAB-MS) provides useful information about higher-nuclearity sulfide clusters, which may be synthesized by a direct synthetic method.  The FAB mass spectrum of the linear trinuclear sulfide cluster 3 shows many ions heavier than the molecular ion.  One envelope corresponds to a pentanuclear sulfide cluster, [{Cp*RhP(OEt)3 (μ-WS4)} 2Cu]+  ([B]+ ).  It was synthesized by the reaction between cluster 2 and Cu+ in a 2:1 molar ratio to yield the compound, [{Cp*RhP(OEt)3 (μ-WS4 )} 2Cu][PF6 ] (9･[PF6 ]).  The structure was determined by a combination of single-crystal X-ray diffraction analysis, Extended X-ray absorption fine structure (EXAFS), and IR measurements. The FAB mass spectrum of 9[PF6+] showed that the cationic cluster [9]+ is identical with [B]+ found in the FAB mass spectrum of 3.  Thus this result suggests that the FAB-MS technique provides useful guiding principal for synthesis of higher nuclearity clusters.", "subitem_description_type": "Other"}]}, "item_1_description_18": {"attribute_name": "フォーマット", "attribute_value_mlt": [{"subitem_description": "application/pdf", "subitem_description_type": "Other"}]}, "item_1_description_7": {"attribute_name": "学位記番号", "attribute_value_mlt": [{"subitem_description": "総研大甲第180号", "subitem_description_type": "Other"}]}, "item_1_select_14": {"attribute_name": "所蔵", "attribute_value_mlt": [{"subitem_select_item": "有"}]}, "item_1_select_8": {"attribute_name": "研究科", "attribute_value_mlt": [{"subitem_select_item": "数物科学研究科"}]}, "item_1_select_9": {"attribute_name": "専攻", "attribute_value_mlt": [{"subitem_select_item": "07 構造分子科学専攻"}]}, "item_1_text_10": {"attribute_name": "学位授与年度", "attribute_value_mlt": [{"subitem_text_value": "1995"}]}, "item_1_text_20": {"attribute_name": "業務メモ", "attribute_value_mlt": [{"subitem_text_value": "（2017年10月25日）本籍など個人情報の記載がある旧要旨・審査要旨を個人情報のない新しいものに差し替えた。"}]}, "item_creator": {"attribute_name": "著者", "attribute_type": "creator", "attribute_value_mlt": [{"creatorNames": [{"creatorName": "OGO, Seiji", "creatorNameLang": "en"}], "nameIdentifiers": [{"nameIdentifier": "7679", "nameIdentifierScheme": "WEKO"}]}]}, "item_files": {"attribute_name": "ファイル情報", "attribute_type": "file", "attribute_value_mlt": [{"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2016-02-17"}], "displaytype": "simple", "download_preview_message": "", "file_order": 0, "filename": "甲180_要旨.pdf", "filesize": [{"value": "317.4 kB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_11", "mimetype": "application/pdf", "size": 317400.0, "url": {"label": "要旨・審査要旨 / Abstract, Screening Result", "url": "https://ir.soken.ac.jp/record/160/files/甲180_要旨.pdf"}, "version_id": "fec42a7c-5423-4c60-9e16-ec55944a183e"}, {"accessrole": "open_date", "date": [{"dateType": "Available", "dateValue": "2016-02-17"}], "displaytype": "simple", "download_preview_message": "", "file_order": 1, "filename": "甲180_本文.pdf", "filesize": [{"value": "10.3 MB"}], "format": "application/pdf", "future_date_message": "", "is_thumbnail": false, "licensetype": "license_11", "mimetype": "application/pdf", "size": 10300000.0, "url": {"label": "本文", "url": "https://ir.soken.ac.jp/record/160/files/甲180_本文.pdf"}, "version_id": "5a983f23-2e9f-4310-bcba-5c409802c7b2"}]}, "item_language": {"attribute_name": "言語", "attribute_value_mlt": [{"subitem_language": "eng"}]}, "item_resource_type": {"attribute_name": "資源タイプ", "attribute_value_mlt": [{"resourcetype": "thesis", "resourceuri": "http://purl.org/coar/resource_type/c_46ec"}]}, "item_title": "Synthesis of Novel Higher-Nuclearity Heterometallic Sulfide Clusters by a Building Block Method", "item_titles": {"attribute_name": "タイトル", "attribute_value_mlt": [{"subitem_title": "Synthesis of Novel Higher-Nuclearity Heterometallic Sulfide Clusters by a Building Block Method"}, {"subitem_title": "Synthesis of Novel Higher-Nuclearity Heterometallic Sulfide Clusters by a Building Block Method", "subitem_title_language": "en"}]}, "item_type_id": "1", "owner": "1", "path": ["9"], "permalink_uri": "https://ir.soken.ac.jp/records/160", "pubdate": {"attribute_name": "公開日", "attribute_value": "2010-02-22"}, "publish_date": "2010-02-22", "publish_status": "0", "recid": "160", "relation": {}, "relation_version_is_last": true, "title": ["Synthesis of Novel Higher-Nuclearity Heterometallic Sulfide Clusters by a Building Block Method"], "weko_shared_id": 1}