JP2004035498A - Water-soluble noble metal complex - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new water-soluble noble metal complex useful as a catalyst for an organic synthetic reaction, a polymerization reaction, or the like. <P>SOLUTION: The water-soluble noble metal complex is represented by molecular formulae: [Pt(CH<SB>3</SB>)<SB>2</SB>(TPPTS)<SB>2</SB>], [Pt(C<SB>2</SB>H<SB>5</SB>)<SB>2</SB>(TPPTS)<SB>2</SB>], [Pt(CH<SB>3</SB>)<SB>2</SB>(THMP)<SB>2</SB>], [Pt(C<SB>2</SB>H<SB>5</SB>)<SB>2</SB>(THMP)<SB>2</SB>], [Pt(C<SB>6</SB>H<SB>5</SB>)<SB>2</SB>(THMP)<SB>2</SB>], [Pt(CH<SB>3</SB>)<SB>2</SB>(DHMPE)], [Pt(C<SB>2</SB>H<SB>5</SB>)<SB>2</SB>(DHMPE)], [Pt(C<SB>6</SB>H<SB>5</SB>)<SB>2</SB>(DHMPE)], [Au(CH<SB>3</SB>)<SB>2</SB>I(TPPTS)], [Au(CH<SB>3</SB>)<SB>2</SB>I(THMP)], [Au(CH<SB>3</SB>)<SB>2</SB>(TPPTS)<SB>2</SB>]<SP>+</SP>I<SP>-</SP>, [Au(CH<SB>3</SB>)<SB>2</SB>(THMP)<SB>2</SB>]<SP>+</SP>I<SP>-</SP>, [Au(CH<SB>3</SB>)<SB>2</SB>(DHMPE)]<SP>+</SP>I<SP>-</SP>, [Rh(CH<SB>3</SB>)(CO)(TPPMS)], [Rh(CH<SB>3</SB>)(CO)(TPPTS)] or [Pd(CH<SB>3</SB>)<SB>2</SB>(TPPTS)<SB>2</SB>] [wherein, TPPTS is 3, 3', 3"-phosphinidine-tris(benzenesulfonic acid)-trisodium; TPPMS is 3-(diphenylphosphino)benzenesulfonic acid-sodium; and THMP is tri(hydroxymethyl)phosphine]. <P>COPYRIGHT: (C)2004,JPO

Description

【０００９】
ＴＰＰＭＳ：
【化２】

【００１０】
ＴＨＭＰ：
【化３】

【００１１】
ＤＨＭＰＥ：
【化４】

【００１２】
反応は、溶媒中、原料の上記公知の貴金属錯体を、ＴＰＰＭＳ、ＴＰＰＴＳ、ＴＨＭＰ又はＤＨＭＰＥと０〜約１００℃の温度で攪拌混合すればよい。当該反応は、通常アルゴン及び窒素等の不活性ガス雰囲気下で行われる。ＴＰＰＭＳ、ＴＰＰＴＳ、ＴＨＭＰ又はＤＨＭＰＥの使用量は、原料である上記公知の貴金属錯体中の貴金属１モルに対してＴＰＰＭＳ、ＴＰＰＴＳ及びＴＨＭＰの場合は通常約２モルであり、ＤＨＭＰＥの場合は通常約１モルである。
【００１３】
反応に使用される溶媒としては、水、メタノール及びエタノール等のアルコール類並びにこれらの混合物等が挙げられる。溶媒の使用量は、原料の貴金属錯体１重量部に対して通常１００〜１０００重量部である。
【００１４】
反応終了後の反応混合物を、所望により濃縮した後、非プロトン性有機溶媒（例えば、アセトン等の脂肪族ケトン、ジエチルエーテル等のエーテル類等）を加えると本発明の水溶性貴金属錯体の沈澱が生成する。生成した沈澱を必要に応じてアルゴン及び窒素等の不活性ガス雰囲気下で濾過すれば、濾滓として本発明の水溶性貴金属錯体が得られる。得られた濾滓の水溶性貴金属錯体は、再結晶又は再沈殿によって精製してもよい。
【００１５】
以下、実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。
なお、以下の実施例においてＩＲスペクトルはＪＡＳＣＯ　ＦＴＩＲ−４１０（日本分光株式会社製）で測定し、ＮＭＲスペクトルはＪＥＯＬ　ＬＡ−３１０（^１Ｈ　３００．４ＭＨｚ）（日本電子株式会社製）で測定し、ケミカルシフトはＤＳＳ（^１Ｈ）と８５％Ｈ_３ＰＯ_４（^３１Ｐ）を基準とした。また元素分析は２４００シリーズＩＩ　ＣＨＮ分析器（パーキンエルマー社製）で行った。ガスはガスクロマトグラフィー（ＧＣ−８Ａ）（株式会社島津製作所製）を用いて、内部標準法で測定した。
【００１６】
実施例１
［Ｐｔ（ＣＨ_３）_２（ＴＰＰＴＳ）_２］の合成
［Ｐｔ（ＣＨ_３）_２（ＣＯＤ）］（８．７ｍｇ，０．０２６ｍｍｏｌ）及びエタノール（１ｍｌ）からなる溶液にＴＰＰＴＳ（３０．４ｍｇ、０．０５３５ｍｍｏｌ）及び水（０．５ｍｌ）からなる溶液を加え、数分間室温で攪拌して無色反応液を得た。尚、反応中に放出された１，５−ＣＯＤは理論量の９５％であった。得られた反応液を濃縮した後、アセトンを加えて白色沈殿を生成させた。これを濾過し、濾滓をヘキサンで洗浄し、次いで減圧乾燥した。水／アセトン＝１／４０（容量比）から再沈殿して、白色結晶を得た。得られた結晶は分析の結果［Ｐｔ（ＣＨ_３）_２（ＴＰＰＴＳ）_２］４水和物であった（収率８０％）。分析結果を以下に示す。
【００１７】
元素分析（Ｃ_３８Ｈ_３８Ｏ_２２Ｎａ_６Ｐ_２ＰｔＳ_６）
計算値：Ｃ　３１．８３％、Ｈ　２．６２％
測定値：Ｃ　３１．８９％、Ｈ　２．９２％
【００１８】
ＩＲ（ＫＢｒ）　ｃｍ^−１：３３３１（νＯＨ），１１９４（ν_ａｓＳＯ），１０３９（ν_ｓＳＯ）
【００１９】
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：０．４２（ｍ，^２Ｊ_Ｈ−Ｐｔ＝６９Ｈｚ，６Ｈ，Ｐｔ−ＣＨ_３），７．３９（ｔ，^３Ｊ_Ｈ−Ｈ＝８Ｈｚ，６Ｈ，５−ＣＨ　芳香環），７．５３（ｔ，^３Ｊ_Ｈ−Ｈ＝^３Ｊ_Ｈ−Ｐ＝８Ｈｚ，６Ｈ，６−ＣＨ　芳香環），７．７６（ｄ，^３Ｊ_Ｈ−Ｈ＝８Ｈｚ，４Ｈ，４−ＣＨ　芳香環），７．７９（ｄ，^３Ｊ_Ｈ−Ｐ＝８Ｈｚ，６Ｈ，２−ＣＨ　芳香環）
【００２０】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：２９．３（ｓ，^１Ｊ_Ｐ−Ｐｔ＝１８５５Ｈｚ）
【００２１】
実施例２
［Ｐｔ（Ｃ_２Ｈ_５）_２（ＴＰＰＴＳ）_２］の合成
実施例１において［Ｐｔ（ＣＨ_３）_２（ＣＯＤ）］に代えて［Ｐｔ（Ｃ_２Ｈ_５）_２（ＣＯＤ）］（７．８ｍｇ，０．０２２ｍｍｏｌ）を用いた以外は実施例１と同様に行い、水／アセトン＝１／４０（容量比）から再沈殿して［Ｐｔ（Ｃ_２Ｈ_５）_２（ＴＰＰＴＳ）_２］の無色粉末をＹ．７２％で得た。［Ｐｔ（Ｃ_２Ｈ_５）_２（ＴＰＰＴＳ）_２］の分析結果を以下に示す。
【００２２】
元素分析（Ｃ_４０Ｈ_４２Ｏ_２２Ｎａ_６Ｐ_２ＰｔＳ_６）
計算値：Ｃ　３２．８６％，Ｈ　２．９０％
測定値：Ｃ　３２．８２％，Ｈ　３．１９％
【００２３】
ＩＲ（ＫＢｒ）　ｃｍ^−１：３４４２（νＯＨ），１１９１（ν_ａｓＳＯ），１０３８（ν_ｓＳＯ）
【００２４】
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：０．７７（ｍ，^３Ｊ_Ｈ−Ｐｔ＝７４Ｈｚ，６Ｈ，Ｐｔ−ＣＨ_２ＣＨ_３），１．１３（ｍ，^２Ｊ_Ｈ−Ｐｔ＝７０Ｈｚ，４Ｈ，Ｐｔ−ＣＨ_２ＣＨ_３），７．３９（ｔ，^３Ｊ_Ｈ−Ｈ＝８Ｈｚ，６Ｈ，５−ＣＨ　芳香環），７．２（ｔ，^３Ｊ_Ｈ−Ｈ＝^３Ｊ_Ｈ−Ｐ＝８Ｈｚ，６Ｈ，６−ＣＨ　芳香環），７．７１（ｄ，^３Ｊ_Ｈ−Ｈ＝８Ｈｚ，６Ｈ，４−ＣＨ　芳香環），７．８５（ｄ，^３Ｊ_Ｈ−Ｐ＝８Ｈｚ，６Ｈ，２−ＣＨ　芳香環）
【００２５】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：２９．０（ｓ，^１Ｊ_Ｐ−Ｐｔ＝１６７７Ｈｚ）
【００２６】
実施例３
［Ｐｔ（ＣＨ_３）_２（ＴＨＭＰ）_２］の合成。
実施例１においてＴＰＰＴＳに代えてＴＨＭＰ（１１．７ｍｇ，０．０９４４ｍｍｏｌ）を用い、［Ｐｔ（ＣＨ_３）_２（ＣＯＤ）］の使用量を１５．８ｍｇ（０．０４７４ｍｍｏｌ）に変えた以外は実施例１と同様に行い［Ｐｔ（ＣＨ_３）_２（ＴＨＭＰ）_２］を収率８２％で得た。［Ｐｔ（ＣＨ_３）_２（ＴＨＭＰ）_２］の分析結果を以下に示す
【００２７】
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６／Ｄ_２Ｏ＝１／５（容量比））δ　ｐｐｍ：０．４９（ｂｒｓ，^２Ｊ_Ｈ−Ｈ＝６６Ｈｚ，６Ｈ，Ｐｔ−ＣＨ_３），４．２９（ｂｒ，１２Ｈ，ＰＣＨ_２ＯＨ）
【００２８】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（ＤＭＳＯ−ｄ_６／Ｄ_２Ｏ＝１／５（容量比））δ　ｐｐｍ：１３．２（ｓ，^１Ｊ_Ｐ−Ｐｔ＝１７００Ｈｚ）
【００２９】
実施例４
［Ｐｔ（Ｃ_２Ｈ_５）_２（ＴＨＭＰ）_２］の合成
実施例１において［Ｐｔ（ＣＨ_３）_２（ＣＯＤ）］に代えて［Ｐｔ（Ｃ_２Ｈ_５）_２（ＣＯＤ）］（１０．９ｍｇ，０．０３０２ｍｍｏｌ）を用い、ＴＰＰＴＳに代えてＴＨＭＰ（７．８ｍｇ，０．０６２９ｍｍｏｌ）を用いた以外は実施例１と同様に行い［Ｐｔ（Ｃ_２Ｈ_５）_２（ＴＨＭＰ）_２］を収率８６％で得た。［Ｐｔ（Ｃ_２Ｈ_５）_２（ＴＨＭＰ）_２］の分析結果を以下に示す。
【００３０】
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６／Ｄ_２Ｏ＝１／５（容量比））δ　ｐｐｍ：１．１４（ｍ，６Ｈ，Ｐｔ−ＣＨ_２ＣＨ_３），１．２（ｑ，^３Ｊ_Ｈ−Ｈ＝８Ｈｚ，^２Ｊ_Ｈ−Ｐｔ＝１２９Ｈｚ，４Ｈ，Ｐｔ−ＣＨ_２ＣＨ_３），４．３３（ｂｒｓ，１２Ｈ，ＰＣＨ_２ＯＨ）
【００３１】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（ＤＭＳＯ−ｄ_６／Ｄ_２Ｏ＝１／５（容量比））δ　ｐｐｍ：８．９（ｓ，^１Ｊ_Ｐ−Ｐｔ＝１４７０Ｈｚ）
【００３２】
実施例５
［Ｐｔ（Ｃ_６Ｈ_５）_２（ＴＨＭＰ）_２］の合成。
実施例１において［Ｐｔ（ＣＨ_３）_２（ＣＯＤ）］に代えて［Ｐｔ（Ｃ_６Ｈ_５）_２（ＣＯＤ）］（１１．３ｍｇ，０．０２４７ｍｍｏｌ）を用い、ＴＰＰＴＳに代えてＴＨＭＰ（５．４ｍｇ，０．０４３６ｍｍｏｌ）を用い、再沈殿の溶媒としてエタノール／ヘキサンを用いた以外は実施例１と同様に行い、［Ｐｔ（Ｃ_６Ｈ_５）_２（ＴＨＭＰ）_２］の白色粉末を収率５８％で得た。尚、反応中に放出された１，５−ＣＯＤは理論量の９２％であった。［Ｐｔ（Ｃ_６Ｈ_５）_２（ＴＨＭＰ）_２］の分析結果を以下に示す。
【００３３】
元素分析（Ｃ_１８Ｈ_２８Ｏ_６Ｐ_２Ｐｔ）
計算値：Ｃ　３６．１９％，Ｈ　４．７２％
測定値：Ｃ　３５．５２％，Ｈ　４．６６％
【００３４】
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：４．０６（ｓ，^２Ｊ_Ｈ−Ｐｔ＝１１Ｈｚ，１２Ｈ，ＰＣＨ_２ＯＨ），６．７９（ｔ，^３Ｊ_Ｈ−Ｈ＝７Ｈｚ，２Ｈ，ｐ−Ｐｈ），７．０１（ｔ，^３Ｊ_Ｈ−Ｈ＝７Ｈｚ，４Ｈ，ｍ−Ｐｈ），７．４１（ｄ，^３Ｊ_Ｈ−Ｈ　＝７Ｈｚ，^３Ｊ_Ｈ−Ｐｔ＝５７Ｈｚ，４Ｈ，ｏ−Ｐｈ）
【００３５】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：４．５（ｓ，^１Ｊ_Ｐ−Ｐｔ＝１６６０Ｈｚ）
【００３６】
実施例６
［Ｐｔ（ＣＨ_３）_２（ＤＨＭＰＥ）］の合成
実施例１においてＴＰＰＴＳに代えてＤＨＭＰＥ（３０．１ｍｇ，０．１４１ｍｍｏｌ）を用い、［Ｐｔ（ＣＨ_３）_２（ＣＯＤ）］の使用量を４７．６ｍｇ（０．１４４ｍｍｏｌ）に変え、再沈殿の溶媒としてエタノール／ヘキサン＝１／２０（容量比）を用いた以外は実施例１と同様に行い、［Ｐｔ（ＣＨ_３）_２（ＤＨＭＰＥ）］の無色粉末を収率６３％で得た。尚、反応中に放出された１，５−ＣＯＤは理論量の１００％であった。［Ｐｔ（ＣＨ_３）_２（ＤＨＭＰＥ）］の分析結果を以下に示す。
【００３７】
元素分析（Ｃ_８Ｈ_２２Ｏ_４Ｐ_２Ｐｔ）
計算値：Ｃ　２１．８７％，Ｈ　５．０５％
測定値：Ｃ　２２．４０％，Ｈ　６．２９％
【００３８】
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：０．５０（ｔ，^３Ｊ_Ｈ−Ｐ＝７Ｈｚ，^２Ｊ_Ｈ−Ｐｔ＝６９Ｈｚ，６Ｈ，Ｐｔ−Ｍｅ），１．９６（ｍ，４Ｈ，ＰＣ_２Ｈ_４），４．１４（ｄｄ，^２Ｊ_Ｈ−Ｈ＝１４Ｈｚ，^３Ｊ_Ｈ−Ｐ＝２．１Ｈｚ，４Ｈ，ＰＣＨ_２ＯＨ），４．２５（ｄ，^２Ｊ_Ｈ−Ｈ＝１４Ｈｚ，^３Ｊ_Ｈ−Ｐｔ＝１２Ｈｚ，４Ｈ，ＰＣＨ_２ＯＨ）
【００３９】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：４９．３（ｓ，^１Ｊ_Ｐ−Ｐｔ＝１６４０Ｈｚ）
【００４０】
実施例７：の合成
［Ｐｔ（Ｃ_２Ｈ_５）_２（ＤＨＭＰＥ）］
実施例１において［Ｐｔ（ＣＨ_３）_２（ＣＯＤ）］に代えて［Ｐｔ（Ｃ_２Ｈ_５）_２（ＣＯＤ）］（１１．３ｍｇ，０．３１３ｍｍｏｌ）を用い、ＴＰＰＴＳに代えてＤＨＭＰＥ（７．２ｍｇ，０．３３６ｍｍｏｌ）を用いた以外は実施例１と同様に行い、［Ｐｔ（Ｃ_２Ｈ_５）_２（ＤＨＭＰＥ）］を収率９１％で得た。尚、反応中に放出された１，５−ＣＯＤは理論量の９４％であった。［Ｐｔ（Ｃ_２Ｈ_５）_２（ＤＨＭＰＥ）］の分析結果を以下に示す。
【００４１】
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６／Ｄ_２Ｏ＝１／５（容量比））δ　ｐｐｍ：１．２５（ｑ，^３Ｊ_Ｈ−Ｈ＝８Ｈｚ，^２Ｊ_Ｈ−Ｐｔ＝７１Ｈｚ，４Ｈ，Ｐｔ−ＣＨ_２ＣＨ_３），１．２６（ｍ，６Ｈ，Ｐｔ−ＣＨ_２ＣＨ_３），１．８８（ｍ，４Ｈ，ＰＣ_２Ｈ_４），４．０９（ｄｄ，^２Ｊ_Ｈ−Ｈ＝１４Ｈｚ，^２Ｊ_Ｈ−Ｐ＝３Ｈｚ，４Ｈ，ＰＣＨ_２ＯＨ），４．２２（ｄ，^２Ｊ_Ｈ−Ｈ＝１４Ｈｚ，^２Ｊ_Ｈ−Ｐｔ＝１１Ｈｚ，４Ｈ，ＰＣＨ_２ＯＨ）
【００４２】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（ＤＭＳＯ−ｄ_６／Ｄ_２Ｏ＝１／５（容量比））δ　ｐｐｍ：４８．３（ｓ，^１Ｊ_Ｐ−Ｐｔ＝１４６０Ｈｚ）
【００４３】
実施例８
［Ｐｔ（Ｃ_６Ｈ_５）_２（ＤＨＭＰＥ）］の合成。
実施例１において［Ｐｄ（ＣＨ_３）_２（ＣＯＤ）］に代えて［Ｐｔ（Ｃ_６Ｈ_５）_２（ＣＯＤ）］（６９．０ｍｇ，０．１５１ｍｍｏｌ）を用い、ＴＰＰＴＳに代えてＤＨＭＰＥ（３２．１ｍｇ，０．１５０ｍｍｏｌ）を用い、再結晶の溶媒としてエタノール／ヘキサンを用いた以外は実施例１と同様に行い、［Ｐｔ（Ｃ_６Ｈ_５）_２（ＤＨＭＰＥ）］の無色粉末を収率６４％で得た。［Ｐｔ（Ｃ_６Ｈ_５）_２（ＤＨＭＰＥ）］の分析結果を以下に示す。
【００４４】
元素分析（Ｃ_１８Ｈ_２６Ｏ_４Ｐ_２Ｐｔ）
計算値：Ｃ　３８．３７％，Ｈ　４．６５％
測定値：Ｃ　３８．３８％，Ｈ　４．８１％
【００４５】
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：２．１０（ｍ，４Ｈ，ＰＣ_２Ｈ_４），４．１１（ｍ，８Ｈ，ＰＣＨ_２ＯＨ），６．８５（ｔ，^３Ｊ_Ｈ−Ｈ＝７Ｈｚ，２Ｈ，ｐ−Ｐｈ），７．０８（ｔ，^３Ｊ_Ｈ−Ｈ＝７Ｈｚ，４Ｈ，ｍ−Ｐｈ），７．４６（ｔ，　^３Ｊ_Ｈ−Ｈ＝^４Ｊ_Ｈ−Ｐ＝７Ｈｚ，^３Ｊ_Ｈ−Ｐｔ＝５２Ｈｚ，４Ｈ，ｏ−Ｐｈ）
【００４６】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：４３．９（ｓ，^１Ｊ_Ｐ−Ｐｔ＝１６００Ｈｚ）
【００４７】
実施例９
ｃｉｓ−［Ａｕ（ＣＨ_３）_２Ｉ（ＴＨＭＰ）］の合成
［Ａｕ（ＣＨ_３）_２Ｉ］_２（３６．６ｍｇ，０．０５１７ｍｍｏｌ）、ＴＨＭＰ（１２．４ｍｇ、０．１００ｍｍｏｌ）をアセトン（３ｍｌ）に溶解し、０℃で３時間攪拌して無色反応液を得た。得られた反応液を濃縮し、次いで溶媒を減圧下に留去した後、減圧乾燥して無色のオイル状物質を得た。得られたオイル状物質は分析の結果ｃｉｓ−［Ａｕ（ＣＨ_３）_２Ｉ（ＴＨＭＰ）］であった（収率１００％）。分析結果を以下に示す。
【００４８】
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：１．１０（ｄ，^３Ｊ_Ｐ−Ｈ＝８．１Ｈｚ，３Ｈ，Ａｕ−ＣＨ_３），１．４４（ｄ，^３Ｊ_Ｐ−Ｈ＝６．９Ｈｚ，３Ｈ，Ａｕ−ＣＨ_３），４．３３（ｂｒｓ，６Ｈ，ＰＣＨ_２），５．４５（ｂｒｓ，３Ｈ，ＯＨ）
【００４９】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：１５．１（ｓ）
【００５０】
実施例１０
ｃｉｓ−［Ａｕ（ＣＨ_３）_２Ｉ（ＴＰＰＴＳ）］の合成
実施例９においてＴＨＭＰに代えてＴＰＰＴＳ（　４８．９ｍｇ，０．０８６０ｍｍｏｌ）および［Ａｕ（ＣＨ_３）_２Ｉ］_２（３０．４ｍｇ、０．０４３０ｍｍｏｌ）を用いた以外は実施例９と同様に行い、ｃｉｓ−［Ａｕ（ＣＨ_３）_２Ｉ（ＴＰＰＴＳ）］の無色粉末を収率９３％で得た。ｃｉｓ−［Ａｕ（ＣＨ_３）_２Ｉ（ＴＰＰＴＳ）］の分析結果を以下に示す。
【００５１】
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ／アセトン−ｄ_６）δ　ｐｐｍ：１．３４（ｄ，^３Ｊ_Ｐ−Ｈ＝８．１Ｈｚ，１Ｈ，Ａｕ−ＣＨ_３），１．４０（ｄ，^３Ｊ_Ｐ−Ｈ＝８．７Ｈｚ，１Ｈ，Ａｕ−ＣＨ_３），７．４−７．９（ｍ，１２Ｈ，ＰＣ_６Ｈ_４）
【００５２】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（Ｄ_２Ｏ／アセトン−ｄ_６）δ　ｐｐｍ：３３．４（ｓ）
【００５３】
実施例１１
［Ａｕ（ＣＨ_３）_２（ＴＨＭＰ）_２］^＋Ｉ⁻の合成
実施例９においてＴＨＭＰの使用量を２４．６ｍｇ（０．１９８ｍｍｏｌ）に、［Ａｕ（ＣＨ_３）_２Ｉ］_２の使用量を（３５．０ｍｇ、０．０４９４ｍｍｏｌ）に変えた以外は実施例９と同様に行い、［Ａｕ（ＣＨ_３）_２（ＴＨＭＰ）_２］^＋Ｉ⁻の無色粉末を収率９２％で得た。［Ａｕ（ＣＨ_３）_２（ＴＨＭＰ）_２］^＋Ｉ⁻の分析結果を以下に示す。
【００５４】
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：１．１４（ｂｒ，６Ｈ，Ａｕ−ＣＨ_３），４．３４（ｂｒ，１２Ｈ，ＰＣＨ_２ＯＨ），５．６２（ｂｒ，６Ｈ，ＰＣＨ２ＯＨ）
【００５５】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：１７．６（ｓ）
【００５６】
実施例１２
［Ａｕ（ＣＨ_３）_２（ＴＰＰＴＳ）_２］^＋Ｉ⁻の合成
実施例９においてＴＨＭＰに代えてＴＰＰＴＳ（１０５．６ｍｇ，０．１８６ｍｍｏｌ）を用い、［Ａｕ（ＣＨ_３）_２Ｉ］_２の使用量を３２．９ｍｇ（０．０４０５ｍｍｏｌ）に変えた以外は実施例９と同様に行い、［Ａｕ（ＣＨ_３）_２（ＴＰＰＴＳ）_２］^＋Ｉ⁻の無色粉末を収率９６％で得た。［Ａｕ（ＣＨ_３）_２（ＴＰＰＴＳ）_２］^＋Ｉ⁻の分析結果を以下に示す。
【００５７】
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：１．０９（ｄ，^３Ｊ_Ｐ−Ｈ＝８Ｈｚ，３Ｈ，ｃｉｓ−Ａｕ−Ｍｅ），１．４５（ｄ，^３Ｊ_Ｐ−Ｈ＝９Ｈｚ，３Ｈ，ｔｒａｎｓ−Ａｕ−Ｍｅ），７．１−７．８（２４Ｈ，ＴＰＰＴＳ）
【００５８】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：３０．２（ｓ），−４．４（ｓ）．
【００５９】
実施例１３
［Ａｕ（ＣＨ_３）_２（ＤＨＭＰＥ）］^＋Ｉ⁻の合成
実施例９においてＴＨＭＰに代えてＤＨＭＰＥ（１８．５ｍｇ，０．０８６４ｍｍｏｌ）を用い、［Ａｕ（ＣＨ_３）_２Ｉ］_２の使用量を（３１．３ｍｇ、０．０４４２ｍｍｏｌ）に変えた以外は実施例９と同様に行い、［Ａｕ（ＣＨ_３）_２（ＤＨＭＰＥ）］^＋Ｉ⁻の無色粉末を収率９５％で得た。［Ａｕ（ＣＨ_３）_２（ＤＨＭＰＥ）］^＋Ｉ⁻の分析結果を以下に示す。
【００６０】
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：１．１３（ｔ，^３Ｊ_Ｐ−Ｈ＝７Ｈｚ，６Ｈ，Ａｕ−ＣＨ_３），２．５１（ｍ，４Ｈ，ＰＣ_２Ｈ_４），４．５４（ｍ，８Ｈ，ＰＣＨ_２ＯＨ）
【００６１】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：５４．４　（ｓ）．
【００６２】
実施例１４
［ＲｈＣＨ_３（ＣＯ）（ＴＰＰＭＳ）_２］の合成
［ＲｈＣＨ_３（ＣＯ）（ＰＰｈ_３）_２］（７１．８ｍｇ，０．１０７ｍｍｏｌ）、ＴＰＰＭＳ（７５．３ｍｇ，０．２０７ｍｍｏｌ）をテトラヒドロフラン（ＴＨＦ）溶媒（４ｍｌ）中、室温で１２時間攪拌して反応させ、黄色けん濁液を得た。上澄みをろ過後、沈殿をＴＨＦ及びベンゼンで洗浄し、次いで減圧乾燥して無色粉末を得た。得られた粉末は分析の結果［ＲｈＭｅ（ＣＯ）（ＴＰＰＭＳ）_２］であった（収率１４％）。分析結果を以下に示す。
【００６３】
ＩＲ（ＫＢｒ）　ｃｍ^−１：１９６０（νＣＯ）；１１９４，１０３９（ν_ａｓ及びν_ｓＳＯ）
【００６４】
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：−０．９５（ｓ，３Ｈ，Ｒｈ−ＣＨ_３），７．１８−７．６９（ｍ，２８Ｈ，Ｐ−Ｃ_６Ｈ_４−５）
【００６５】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：４２．８（ｄ，^１Ｊ_Ｐ−Ｒｈ＝１５７Ｈｚ）
【００６６】
実施例１５
［Ｒｈ（ＣＨ_３）（ＣＯ）（ＴＰＰＴＳ）_２］の合成
実施例１４においてＴＰＰＭＳに代えてＴＰＰＴＳ（２９．３ｍｇ，０．０４３７ｍｍｏｌ）を用い、溶媒をＴＨＦ（３ｍｌ）／メタノール（５０ｍｌ）に代えた以外は実施例１４と同様に行った。得られた橙色けん濁液を濃縮した後ろ過し、濾滓として［Ｒｈ（ＣＨ_３）（ＣＯ）（ＴＰＰＴＳ）_２］の黄色粉末を収率７７％で得た。
【００６７】
ＩＲ（ＫＢｒ）　ｃｍ^−１：１９４９（νＣＯ）；１１９５，１０４０（ν_ａｓ及びν_ｓＳＯ）
【００６８】
^１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：−１．０３（ｓ，３Ｈ，Ｒｈ−ＣＨ_３），７．０４−７．６０（ｍ，２４Ｈ，Ｐ−Ｃ_６Ｈ_４−５）
【００６９】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（ＤＭＳＯ−ｄ_６）δ　ｐｐｍ：４３．９（ｄ，^１Ｊ_Ｐ−Ｒｈ＝１５６Ｈｚ）
【００７０】
実施例１６
［Ｐｄ（ＣＨ_３）_２（ＴＰＰＴＳ）_２］の合成
［Ｐｔ（ＣＨ_３）_２（ＴＭＥＤＡ）］（７．６ｍｇ，０．０３０ｍｍｏｌ）及びＤＭＳＯ（０．５ｍｌ）からなる溶液にＴＰＰＴＳ（３３．２ｍｇ、０．０５８５ｍｍｏｌ）を加え、数分間室温で攪拌して無色反応液を得た。得られた反応液にアセトン（１０ｍｌ）を加えて白色沈殿を生成させた。これを濾過し、濾滓をアセトン（１ｍｌ）で３回洗浄し、次いで減圧乾燥して白色粉末を得た。得られた粉末は分析の結果［Ｐｄ（ＣＨ_３）_２（ＴＰＰＴＳ）_２］であった（収率９０％）。分析結果を以下に示す。
【００７１】
^１Ｈ−ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：０．１７（ｍ，６Ｈ，Ｐｄ−ＣＨ_３），７．３−８．１（ｍ，２４Ｈ，芳香環）
【００７２】
^３１Ｐ｛^１Ｈ｝ＮＭＲ（Ｄ_２Ｏ）δ　ｐｐｍ：２８．８（ｓ）[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel water-soluble noble metal complex, and more particularly to a water-soluble noble metal complex of Rh, Au, Pt or Pd. The water-soluble noble metal complex of the present invention is an industrially useful compound as a catalyst for an organic synthesis reaction, a polymerization reaction, or the like.
[0002]
[Prior art]
The water-soluble noble metal complex of the present invention is a novel compound not described in any literature.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel water-soluble noble metal complex useful as a catalyst for an organic synthesis reaction, a polymerization reaction, and the like.
[0004]
[Means for Solving the Problems]
The present inventors have intensively studied to solve the above problems. As a result, a novel water-soluble noble metal complex represented by the following molecular formula was found.
[Pt (CH ₃ ) ₂ (TPPTS) ₂ ], [Pt (C ₂ H ₅ ) ₂ (TPPTS) ₂ ], [Pt (CH ₃ ) ₂ (THMP) ₂ ], [Pt (C ₂ H ₅ ) _{2] (THMP) 2], [Pt} (C 6 H 5) 2 (THMP) 2], [Pt (CH 3) 2 (DHMPE)], [Pt (C 2 H 5) 2 (DHMPE)], [Pt ( _{C 6 H 5) 2 (DHMPE} )], [Au (CH 3) 2 I (TPPTS)], [Au (CH 3) 2 I (THMP)], [Au (CH 3) 2 (TPPTS) 2] + _{^{I -, [Au (CH 3}} ) 2 (THMP) 2] + I -, [Au (CH 3) 2 (DHMPE)] + I -, [Rh (CH 3) (CO) (TPPMS)], [Rh (CH ₃ ) (CO) (TPPTS)] or [Pd (CH ₃₎ ) ₂ (TPPTS) ₂ ]
Wherein TPPTS is 3,3 ', 3 "-phosphinidine tris (benzenesulfonic acid) = trisodium, TPPMS is 3- (diphenylphosphino) benzenesulfonic acid = sodium, and THMP is tri (hydroxymethyl ) Phosphine, and DHMPE represents 1,2-bisdi (hydroxymethyl) phosphinodiethane.]
[0005]
That is, the present invention relates to a water-soluble noble metal complex represented by the following molecular formula.
[Pt (CH ₃ ) ₂ (TPPTS) ₂ ], [Pt (C ₂ H ₅ ) ₂ (TPPTS) ₂ ], [Pt (CH ₃ ) ₂ (THMP) ₂ ], [Pt (C ₂ H ₅ ) _{2] (THMP) 2], [Pt} (C 6 H 5) 2 (THMP) 2], [Pt (CH 3) 2 (DHMPE)], [Pt (C 2 H 5) 2 (DHMPE)], [Pt ( _{C 6 H 5) 2 (DHMPE} )], [Au (CH 3) 2 I (TPPTS)], [Au (CH 3) 2 I (THMP)], [Au (CH 3) 2 (TPPTS) 2] + _{^{I -, [Au (CH 3}} ) 2 (THMP) 2] + I -, [Au (CH 3) 2 (DHMPE)] + I -, [Rh (CH 3) (CO) (TPPMS)], [Rh (CH ₃ ) (CO) (TPPTS)] or [Pd (CH ₃₎ ) ₂ (TPPTS) ₂ ]
[0006]
The water-soluble noble metal complex of the present invention is water-soluble and can be stably present in water. Therefore, according to the present invention, when the target substance is a poorly water-soluble compound in a conventional reaction using a noble metal complex as a catalyst, if the water-soluble noble metal complex of the present invention is used as a catalyst, the reaction mixture after the reaction is completed The target substance and the water-soluble noble metal complex of the present invention can be separated and easily recovered. That is, for example, using the water-soluble noble metal complex of the present invention as a catalyst and performing the reaction in water-hydrophobic organic solvent, in the reaction mixture after the reaction, the water-soluble noble metal complex of the present invention in the aqueous layer, Since the target substance is dissolved in the organic solvent layer, the aqueous layer and the organic solvent layer can be separated to easily separate and recover the catalyst and the target substance. The simple precious metal complex can be reused as it is as a catalyst for the reaction, so that a simple and industrial organic compound production process can be constructed.
[0007]
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in detail below.
The water-soluble noble metal complex of the present invention is, for example, a known alkyl or aryl complex of Rh, Au, Pt and Pd, for example, a molecular formula [Rh (CH ₃ ) (CO) (PPh ₃ ) ₂ ] (where PPh ₃ represents triphenylphosphine), [Au (CH ₃ ) ₂ I] ₂ , [PtR ₂ (COD)] (wherein R represents a methyl group, an ethyl group or a phenyl group, and COD represents 1,5- Which represents cyclooctadiene (the same applies hereinafter), Pd [(CH ₃ ) ₂ (TMEDA)], etc., and uses these as a water-soluble ligand of the water-soluble noble metal complex of the present invention; Of TPPMS, TPPTS, THMP or DHMPE.
[0008]
TPPTS:
Embedded image

[0009]
TPPMS:
Embedded image

[0010]
THMP:
Embedded image

[0011]
DHMPE:
Embedded image

[0012]
The reaction may be performed by stirring and mixing the above-mentioned known noble metal complex as a raw material with TPPMS, TPPTS, THMP or DHMPE in a solvent at a temperature of 0 to about 100 ° C. The reaction is usually performed under an atmosphere of an inert gas such as argon and nitrogen. The amount of TPPMS, TPPTS, THMP or DHMPE used is usually about 2 moles in the case of TPPMS, TPPTS and THMP, and usually about 1 mole in the case of TPPMS, TPPTS and THMP per mole of the noble metal in the known noble metal complex as a raw material. Is a mole.
[0013]
Examples of the solvent used in the reaction include water, alcohols such as methanol and ethanol, and mixtures thereof. The amount of the solvent used is usually 100 to 1000 parts by weight per 1 part by weight of the noble metal complex as the raw material.
[0014]
After the reaction mixture after completion of the reaction is concentrated as required, an aprotic organic solvent (for example, an aliphatic ketone such as acetone, or an ether such as diethyl ether or the like) is added to precipitate the water-soluble noble metal complex of the present invention. Generate. If necessary, the resulting precipitate is filtered under an atmosphere of an inert gas such as argon and nitrogen to obtain the water-soluble noble metal complex of the present invention as a filter cake. The obtained water-soluble noble metal complex of the filter cake may be purified by recrystallization or reprecipitation.
[0015]
Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.
Incidentally, IR spectra were measured with a JASCO FTIR-410 (manufactured by JASCO Corporation) in the following examples, NMR spectra were measured with a ^{JEOL LA-310 (1 H 300.4MHz} ) ( manufactured by JEOL Ltd.), Chemical shifts were referenced to DSS ⁽¹ H) and ^{_{85% H 3 PO 4 (31}} P). Elemental analysis was performed using a 2400 series II CHN analyzer (manufactured by PerkinElmer). The gas was measured by an internal standard method using gas chromatography (GC-8A) (manufactured by Shimadzu Corporation).
[0016]
Example 1
Synthesis of [Pt (CH ₃ ) ₂ (TPPTS) ₂ ] To a solution consisting of [Pt (CH ₃ ) ₂ (COD)] (8.7 mg, 0.026 mmol) and ethanol (1 ml) was added TPPTS (30.4 mg, 0 ml). (0.0535 mmol) and water (0.5 ml) were added and stirred at room temperature for several minutes to obtain a colorless reaction solution. The 1,5-COD released during the reaction was 95% of the theoretical amount. After concentrating the obtained reaction solution, acetone was added to generate a white precipitate. This was filtered, the cake was washed with hexane, and then dried under reduced pressure. Reprecipitation from water / acetone = 1/40 (volume ratio) gave white crystals. The obtained crystals were analyzed to be [Pt (CH ₃ ) ₂ (TPPTS) ₂ ] tetrahydrate (yield 80%). The analysis results are shown below.
[0017]
Elemental analysis _{(C 38 H 38 O 22 Na} 6 P 2 PtS 6)
Calculated value: C 31.83%, H 2.62%
Measured value: C 31.89%, H 2.92%
[0018]
IR (KBr) cm ⁻¹ : 3331 (νOH), 1194 (ν _as SO), 1039 (ν _s SO)
[0019]
¹ H-NMR (D ₂ O) δ ppm: 0.42 (m, ² J _H-Pt = 69 Hz, 6H, Pt-CH ₃ ), 7.39 (t, ³ J _H-H = 8 Hz, 6 _H , 5-CH aromatic _{^{ring), 7.53 (t, 3 J}} H-H = 3 J H-P = 8Hz, 6H, 6-CH aromatic _{^{ring), 7.76 (d, 3 J}} H-H = 8Hz, 4H, 4-CH aromatic _{^{ring), 7.79 (d, 3 J}} H-P = 8Hz, 6H, 2-CH aromatic)
[0020]
³¹ P { ¹ H} NMR (D ₂ O) δ ppm: 29.3 (s, ¹ JP _-Pt = 1855 Hz)
[0021]
Example 2
_{[Pt (C 2 H 5)} 2 (TPPTS) 2] Synthesis Example 1 in place of _{[Pt (CH 3) 2 (} COD)] [Pt (C 2 H 5) 2 (COD)] (7. The same procedure as in Example 1 was carried out except that 8 mg, 0.022 mmol) was used, and the precipitate was reprecipitated from water / acetone = 1/40 (volume ratio) to obtain [Pt (C ₂ H ₅ ) ₂ (TPPTS) ₂ ]. A colorless powder was obtained from Y. Obtained at 72%. The analysis results of [Pt (C ₂ H ₅ ) ₂ (TPPTS) ₂ ] are shown below.
[0022]
Elemental analysis _{(C 40 H 42 O 22 Na} 6 P 2 PtS 6)
Calculated value: C 32.86%, H 2.90%
Measured value: C: 32.82%, H: 3.19%
[0023]
IR (KBr) cm ^-1 : 3442 (νOH), 1191 (ν _as SO), 1038 (ν _s SO)
[0024]
¹ H-NMR (D ₂ O) δ ppm: 0.77 (m, ³ J _H-Pt = 74 Hz, 6 H, Pt-CH ₂ CH ₃ ), 1.13 (m, ² J _H-Pt = 70 Hz, ^{_{4H, Pt-CH 2 CH 3}} ), 7.39 (t, 3 J H-H = 8Hz, 6H, 5-CH aromatic _{^{ring), 7.2 (t, 3 J}} H-H = 3 J H-P = 8 Hz, 6H, 6-CH aromatic ring), 7.71 (d, ³ _JH-H = 8 Hz, 6H, 4-CH aromatic ring), 7.85 (d, ³ _JH-P = 8 Hz, 6H , 2-CH aromatic ring)
[0025]
³¹ P { ¹ H} NMR (D ₂ O) δ ppm: 29.0 (s, ¹ JP _-Pt = 1677 Hz)
[0026]
Example 3
Synthesis of [Pt (CH ₃ ) ₂ (THMP) ₂ ].
Example 1 was repeated except that THMP (11.7 mg, 0.0944 mmol) was used in place of TPPTS and the amount of [Pt (CH ₃ ) ₂ (COD)] was changed to 15.8 mg (0.0474 mmol). [Pt (CH ₃ ) ₂ (THMP) ₂ ] was obtained in a yield of 82% in the same manner as in Example 1. The analysis results of [Pt (CH ₃ ) ₂ (THMP) ₂ ] are shown below.
_{^{1 H-NMR (DMSO-d}} 6 / D 2 O = 1/5 ( volume ^{ratio)) δ ppm: 0.49 (brs} , 2 J H-H = 66Hz, 6H, Pt-CH 3), 4.29 (Br, 12H, PCH ₂ OH)
[0028]
³¹ P { ¹ H} NMR (DMSO-d ₆ / D ₂ O = 1/5 (volume ratio)) δ ppm: 13.2 (s, ¹ JP _-Pt = 1700 Hz)
[0029]
Example 4
_{[Pt (C 2 H 5)} 2 (THMP) 2] [Pt (CH 3) 2 (COD)] instead of _{[Pt (C 2 H 5)} 2 (COD)] Synthesis Example 1 (10. 9 mg, 0.0302 mmol) and [Pt (C ₂ H ₅ ) ₂ (THMP) ₂ ] was conducted in the same manner as in Example 1 except that THMP (7.8 mg, 0.0629 mmol) was used instead of TPPTS. Obtained in 86% yield. The analysis results of [Pt (C ₂ H ₅ ) ₂ (THMP) ₂ ] are shown below.
[0030]
¹ H-NMR (DMSO-d ₆ / D ₂ O = 1/5 (volume ratio)) δ ppm: 1.14 (m, 6H, Pt-CH ₂ CH ₃ ), 1.2 (q, ³ _{JH) ^{-H = 8Hz, 2 J H-}} Pt = 129Hz, 4H, Pt-CH 2 CH 3), 4.33 (brs, 12H, PCH 2 OH)
[0031]
³¹ P { ¹ H} NMR (DMSO-d ₆ / D ₂ O = 1/5 (volume ratio)) δ ppm: 8.9 (s, ¹ JP _-Pt = 1470 Hz)
[0032]
Example 5
Synthesis of [Pt (C ₆ H ₅ ) ₂ (THMP) ₂ ].
In Example 1, [Pt (C ₆ H ₅ ) ₂ (COD)] (11.3 mg, 0.0247 mmol) was used instead of [Pt (CH ₃ ) ₂ (COD)], and THMP (5) was used instead of TPPTS. .4 mg, 0.0436 mmol), and the same procedure as in Example 1 was carried out except that ethanol / hexane was used as a reprecipitation solvent, to collect a white powder of [Pt (C ₆ H ₅ ) ₂ (THMP) ₂ ]. Obtained at a rate of 58%. The 1,5-COD released during the reaction was 92% of the theoretical amount. The analysis results of [Pt (C ₆ H ₅ ) ₂ (THMP) ₂ ] are shown below.
[0033]
Elemental analysis _{(C 18 H 28 O 6 P} 2 Pt)
Calculated value: C 36.19%, H 4.72%
Measured value: C 35.52%, H 4.66%
[0034]
¹ H-NMR (D ₂ O) δ ppm: 4.06 (s, ² J _H-Pt = 11 Hz, 12 H, PCH ₂ OH), 6.79 (t, ³ J _H-H = 7 Hz, 2 H, p _{^{-Ph), 7.01 (t, 3}} J H-H = 7Hz, 4H, m-Ph), 7.41 (d, 3 J H-H = 7Hz, 3 J H-Pt = 57Hz, 4H, o -Ph)
[0035]
³¹ P { ¹ H} NMR (D ₂ O) δ ppm: 4.5 (s, ¹ JP _-Pt = 1660 Hz)
[0036]
Example 6
Synthesis of [Pt (CH ₃ ) ₂ (DHMPE)] In Example 1, DHMPE (30.1 mg, 0.141 mmol) was used instead of TPPTS, and the amount of [Pt (CH ₃ ) ₂ (COD)] used was 47. [Pt (CH ₃ ) ₂ (DHMPE)], except that the amount was changed to 0.6 mg (0.144 mmol) and ethanol / hexane = 1/20 (volume ratio) was used as a solvent for reprecipitation. Was obtained in a yield of 63%. The 1,5-COD released during the reaction was 100% of the theoretical amount. The analysis results of [Pt (CH ₃ ) ₂ (DHMPE)] are shown below.
[0037]
Elemental analysis _{(C 8 H 22 O 4 P} 2 Pt)
Calculated value: C 21.87%, H 5.05%
Measured value: C 22.40%, H 6.29%
[0038]
¹ H-NMR (D ₂ O) δ ppm: 0.50 (t, ³ J _H-P = 7 Hz, ² J _H-Pt = 69 Hz, 6 H, Pt-Me), 1.96 (m, 4 H, PC ^{_{2 H 4), 4.14 (dd}} , 2 J H-H = 14Hz, 3 J H-P = 2.1Hz, 4H, PCH 2 OH), 4.25 (d, 2 J H-H = 14Hz, _{^{3 J H-Pt = 12Hz,}} 4H, PCH 2 OH)
[0039]
³¹ P { ¹ H} NMR (D ₂ O) δ ppm: 49.3 (s, ¹ JP _-Pt = 1640 Hz)
[0040]
Synthesis of Example 7: [Pt (C ₂ H ₅ ) ₂ (DHMPE)]
In Example 1, [Pt (C ₂ H ₅ ) ₂ (COD)] (11.3 mg, 0.313 mmol) was used instead of [Pt (CH ₃ ) ₂ (COD)], and DHMPE (7) was used instead of TPPTS. [Pt (C ₂ H ₅ ) ₂ (DHMPE)] in a yield of 91%. The 1,5-COD released during the reaction was 94% of the theoretical amount. The analysis results of [Pt (C ₂ H ₅ ) ₂ (DHMPE)] are shown below.
[0041]
¹ H-NMR (DMSO-d ₆ / D ₂ O = 1/5 (volume ratio)) δ ppm: 1.25 (q, ³ J _H−H = 8 Hz, ² J _H−Pt = 71 Hz, 4 H, Pt) _{-CH 2 CH 3), 1.26 (} m, 6H, Pt-CH 2 CH 3), 1.88 (m, 4H, PC 2 H 4), 4.09 (dd, 2 J H-H = 14Hz _{^{, 2 J H-P = 3Hz}} , 4H, PCH 2 OH), 4.22 (d, 2 J H-H = 14Hz, 2 J H-Pt = 11Hz, 4H, PCH 2 OH)
[0042]
³¹ P { ¹ H} NMR (DMSO-d ₆ / D ₂ O = 1/5 (volume ratio)) δ ppm: 48.3 (s, ¹ JP _-Pt = 1460 Hz)
[0043]
Example 8
Synthesis of [Pt (C ₆ H ₅ ) ₂ (DHMPE)].
In Example 1, [Pt (C ₆ H ₅ ) ₂ (COD)] (69.0 mg, 0.151 mmol) was used instead of [Pd (CH ₃ ) ₂ (COD)], and DHMPE (32) was used instead of TPPTS. .1 mg, 0.150 mmol) and the same procedure as in Example 1 except that ethanol / hexane was used as a solvent for recrystallization to obtain a colorless powder of [Pt (C ₆ H ₅ ) ₂ (DHMPE)]. Obtained at 64%. The analysis results of [Pt (C ₆ H ₅ ) ₂ (DHMPE)] are shown below.
[0044]
Elemental analysis _{(C 18 H 26 O 4 P} 2 Pt)
Calculated value: C 38.37%, H 4.65%
Measured value: C 38.38%, H 4.81%
[0045]
¹ H-NMR (D ₂ O) δ ppm: 2.10 (m, 4H, PC ₂ H ₄ ), 4.11 (m, 8 H, PCH ₂ OH), 6.85 (t, ³ J _{H-H) ^{= 7Hz, 2H, p-Ph}} ), 7.08 (t, 3 J H-H = 7Hz, 4H, m-Ph), 7.46 (t, 3 J H-H = 4 J H-P = 7Hz , ³ J _H-Pt = 52 Hz, 4H, o-Ph)
[0046]
³¹ P { ¹ H} NMR (D ₂ O) δ ppm: 43.9 (s, ¹ JP _-Pt = 1600 Hz)
[0047]
Example 9
Synthesis of cis- [Au (CH ₃ ) ₂ I (THMP)] [Au (CH ₃ ) ₂ I] ₂ (36.6 mg, 0.0517 mmol) and THMP (12.4 mg, 0.100 mmol) in acetone (3 ml) ) And stirred at 0 ° C. for 3 hours to obtain a colorless reaction solution. The obtained reaction solution was concentrated, then the solvent was distilled off under reduced pressure, and then dried under reduced pressure to obtain a colorless oily substance. As a result of analysis, the obtained oily substance was cis- [Au (CH ₃ ) ₂ I (THMP)] (yield 100%). The analysis results are shown below.
[0048]
¹ H-NMR (DMSO-d ₆ ) δ ppm: 1.10 (d, ³ JP _-H = 8.1 Hz, 3 H, Au-CH ₃ ), 1.44 (d, ³ JP _-H = 6) _{.9Hz, 3H, Au-CH 3} ), 4.33 (brs, 6H, PCH 2), 5.45 (brs, 3H, OH)
[0049]
³¹ P { ¹ H} NMR (DMSO-d ₆ ) δ ppm: 15.1 (s)
[0050]
Example 10
Synthesis of cis- [Au (CH ₃ ) ₂ I (TPPTS)] In Example 9, TPPTS (48.9 mg, 0.0860 mmol) and [Au (CH ₃ ) ₂ I] ₂ (30.4 mg, Except for using 0.0430 mmol), the same procedure as in Example 9 was carried out to obtain a colorless powder of cis- [Au (CH ₃ ) ₂ I (TPPTS)] at a yield of 93%. The analysis results of cis- [Au (CH ₃ ) ₂ I (TPPTS)] are shown below.
[0051]
_{^{1 H-NMR (D 2 O}} / acetone ^{_{-d 6) δ ppm: 1.34 (}} d, 3 J P-H = 8.1Hz, 1H, Au-CH 3), 1.40 (d, 3 J P _{-H = 8.7Hz, 1H, Au-} CH 3), 7.4-7.9 (m, 12H, PC 6 H 4)
[0052]
³¹ P { ¹ H} NMR (D ₂ O / acetone-d ₆ ) δ ppm: 33.4 (s)
[0053]
Example 11
Synthesis of [Au (CH ₃ ) ₂ (THMP) ₂ ] ⁺ I ^{− In} Example 9, the amount of THMP used was 24.6 mg (0.198 mmol), and the amount of [Au (CH ₃ ) ₂ I] ₂ used was (35.0 mg, 0.0494 mmol) was carried out in the same manner as in Example 9 to obtain a colorless powder of [Au (CH ₃ ) ₂ (THMP) ₂ ] ⁺ I ⁻ with a yield of 92%. _{[Au (CH 3) 2 (} THMP) 2] + I - shows the result of analysis below.
[0054]
_{^{1 H-NMR (DMSO-d}} 6) δ ppm: 1.14 (br, 6H, Au-CH 3), 4.34 (br, 12H, PCH 2 OH), 5.62 (br, 6H, PCH2OH)
[0055]
³¹ P { ¹ H} NMR (DMSO-d ₆ ) δ ppm: 17.6 (s)
[0056]
Example 12
Synthesis of [Au (CH ₃ ) ₂ (TPPTS) ₂ ] ⁺ I ^{− In} Example 9, TPPTS (105.6 mg, 0.186 mmol) was used instead of THMP, and [Au (CH ₃ ) ₂ I] ₂ was used. Except that the amount was changed to 32.9 mg (0.0405 mmol), the same procedures as in Example 9 were carried out to obtain a colorless powder of [Au (CH ₃ ) ₂ (TPPTS) ₂ ] ⁺ I ⁻ with a yield of 96%. _{[Au (CH 3) 2 (} TPPTS) 2] + I - shows the result of analysis below.
[0057]
¹ H-NMR (DMSO-d ₆ ) δ ppm: 1.09 (d, ³ JP _-H = 8 Hz, 3 H, cis-Au-Me), 1.45 (d, ³ JP _-H = 9 Hz, 3H, trans-Au-Me), 7.1-7.8 (24H, TPPTS).
[0058]
³¹ P { ¹ H} NMR (DMSO-d ₆ ) δ ppm: 30.2 (s), -4.4 (s).
[0059]
Example 13
Synthesis of [Au (CH ₃ ) ₂ (DHMPE)] ⁺ I ^{− In} Example 9, DHMPE (18.5 mg, 0.0864 mmol) was used instead of THMP, and the amount of [Au (CH ₃ ) ₂ I] ₂ used Was changed to (31.3 mg, 0.0442 mmol) in the same manner as in Example 9 to obtain a colorless powder of [Au (CH ₃ ) ₂ (DHMPE)] ⁺ I ^{− in} a yield of 95%. The analysis results of [Au (CH ₃ ) ₂ (DHMPE)] ⁺ I ⁻ are shown below.
[0060]
_3. ¹ H-NMR (D ₂ O) δ ppm: 1.13 (t, ³ JP _-H = 7 Hz, 6 _H , Au-CH ₃ ), 2.51 (m, 4 H, PC ₂ H ₄ ), 4. 54 (m, 8H, PCH ₂ OH)
[0061]
³¹ P { ¹ H} NMR (D ₂ O) δ ppm: 54.4 (s).
[0062]
Example 14
Synthesis of [RhCH ₃ (CO) (TPPMS) ₂ ] [RhCH ₃ (CO) (PPh ₃ ) ₂ ] (71.8 mg, 0.107 mmol) and TPPMS (75.3 mg, 0.207 mmol) in tetrahydrofuran (THF) The mixture was stirred and reacted in a solvent (4 ml) at room temperature for 12 hours to obtain a yellow suspension. After filtering the supernatant, the precipitate was washed with THF and benzene, and then dried under reduced pressure to obtain a colorless powder. As a result of analysis, the obtained powder was [RhMe (CO) (TPPMS) ₂ ] (yield: 14%). The analysis results are shown below.
[0063]
IR (KBr) cm ^-1 : 1960 (νCO); 1194, 1039 (ν _as and ν _s SO)
[0064]
_{^{1 H-NMR (DMSO-d}} 6) δ ppm: -0.95 (s, 3H, Rh-CH 3), 7.18-7.69 (m, 28H, P-C 6 H 4-5)
[0065]
³¹ P { ¹ H} NMR (DMSO-d ₆ ) δ ppm: 42.8 (d, ¹ JP _-Rh = 157 Hz)
[0066]
Example 15
Synthesis of [Rh (CH ₃ ) (CO) (TPPTS) ₂ ] In Example 14, TPPTS (29.3 mg, 0.0437 mmol) was used instead of TPPMS, and the solvent was changed to THF (3 ml) / methanol (50 ml). The procedure was performed in the same manner as in Example 14 except for the above. The obtained orange suspension was concentrated and then filtered to obtain a yellow powder of [Rh (CH ₃ ) (CO) (TPPTS) ₂ ] as a filter residue in a yield of 77%.
[0067]
IR (KBr) cm ^-1 : 1949 (νCO); 1195, 1040 (ν _as and ν _s SO)
[0068]
_{^{1 H-NMR (DMSO-d}} 6) δ ppm: -1.03 (s, 3H, Rh-CH 3), 7.04-7.60 (m, 24H, P-C 6 H 4-5)
[0069]
³¹ P { ¹ H} NMR (DMSO-d ₆ ) δ ppm: 43.9 (d, ¹ JP _-Rh = 156 Hz)
[0070]
Example 16
Synthesis of [Pd (CH ₃ ) ₂ (TPPTS) ₂ ] To a solution consisting of [Pt (CH ₃ ) ₂ (TMEDA)] (7.6 mg, 0.030 mmol) and DMSO (0.5 ml) was added TPPTS (33.2 mg). , 0.0585 mmol) and stirred at room temperature for several minutes to give a colorless reaction solution. Acetone (10 ml) was added to the obtained reaction solution to produce a white precipitate. This was filtered, and the filter cake was washed three times with acetone (1 ml) and then dried under reduced pressure to obtain a white powder. As a result of analysis, the obtained powder was [Pd (CH ₃ ) ₂ (TPPTS) ₂ ] (yield 90%). The analysis results are shown below.
[0071]
¹ H-NMR (D ₂ O) δ ppm: 0.17 (m, 6H, Pd-CH ₃ ), 7.3-8.1 (m, 24H, aromatic ring)
[0072]
³¹ P { ¹ H} NMR (D ₂ O) δ ppm: 28.8 (s)

Claims (1)

A water-soluble noble metal complex represented by the following molecular formula.
[Pt (CH ₃ ) ₂ (TPPTS) ₂ ], [Pt (C ₂ H ₅ ) ₂ (TPPTS) ₂ ], [Pt (CH ₃ ) ₂ (THMP) ₂ ], [Pt (C ₂ H ₅ ) _{2] (THMP) 2], [Pt} (C 6 H 5) 2 (THMP) 2], [Pt (CH 3) 2 (DHMPE)], [Pt (C 2 H 5) 2 (DHMPE)], [Pt ( _{C 6 H 5) 2 (DHMPE} )], [Au (CH 3) 2 I (TPPTS)], [Au (CH 3) 2 I (THMP)], [Au (CH 3) 2 (TPPTS) 2] + ^{_{I -, [Au (CH 3}} ) 2 (THMP) 2] + I -, [Au (CH 3) 2 (DHMPE)] + I -, [Rh (CH 3) (CO) (TPPMS)], [Rh (CH ₃ ) (CO) (TPPTS)] or [Pd (CH ₃₎ ) ₂ (TPPTS) ₂ ]
Wherein TPPTS is 3,3 ', 3 "-phosphinidine tris (benzenesulfonic acid) = trisodium, TPPMS is 3- (diphenylphosphino) benzenesulfonic acid = sodium, and THMP is tri (hydroxymethyl ) Phosphine, and DHMPE represents 1,2-bisdi (hydroxymethyl) phosphinodiethane.]