{"id":55319,"date":"2025-03-11T08:00:29","date_gmt":"2025-03-11T00:00:29","guid":{"rendered":"\/\/www.gsbet888.com\/?p=55319"},"modified":"2025-03-11T19:51:18","modified_gmt":"2025-03-11T11:51:18","slug":"jacs%ef%bc%9a%e5%8f%8c%e9%93%91-%e9%92%af%e5%8f%8c%e9%87%8d%e5%82%ac%e5%8c%96113%e7%8e%af%e5%8c%96%e5%8f%8d%e5%ba%94","status":"publish","type":"post","link":"\/\/www.gsbet888.com\/%e5%8c%96%e5%ad%a6%e6%9d%82%e8%ae%b0\/recentpaper\/2025\/03\/jacs%ef%bc%9a%e5%8f%8c%e9%93%91-%e9%92%af%e5%8f%8c%e9%87%8d%e5%82%ac%e5%8c%96113%e7%8e%af%e5%8c%96%e5%8f%8d%e5%ba%94.html","title":{"rendered":"JACS\uff1a\u53cc\u94d1-\u94af\u53cc\u91cd\u50ac\u5316[1+1+3]\u73af\u5316\u53cd\u5e94"},"content":{"rendered":"

\u4f5c\u8005\uff1a\u6749\u6749<\/p>\n

\u5bfc\u8bfb\uff1a<\/h4>\n

\u8fd1\u65e5\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u4e0a\u6d77\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\u738b\u6653\u660e\u8bfe\u9898\u7ec4\u5728J. Am. Chem. Soc.<\/em>\u4e2d\u53d1\u8868\u8bba\u6587\uff0c\u62a5\u9053\u4e00\u79cd\u9ad8\u6548\u7684\u91cd\u6c2e\u5316\u5408\u7269\u3001\u70ef\u4e19\u57fa\u4e8c\u4e59\u9178\u916f(allylic diacetates)\u4e0e\u82ef\u80fa(\u6216H2<\/sub>O)\u7684\u4e09\u7ec4\u5206\u53cd\u5e94\uff0c\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u7ed3\u6784\u591a\u6837\u7684\u5421\u54af\u70f7\u4e0e\u56db\u6c22\u544b\u5583\u884d\u751f\u7269\u3002\u540c\u65f6\uff0c\u8fd9\u79cd\u5f62\u5f0f\u7684[1+1+3]\u73af\u5316\u53cd\u5e94\u5177\u6709\u9ad8\u6548\u3001\u9ad8\u4ea7\u7387\u4e0e\u5e7f\u6cdb\u7684\u5b98\u80fd\u56e2\u76f8\u5bb9\u6027\u7b49\u7279\u70b9\uff0c\u5e76\u53ef\u7528\u4e8e\u51e0\u79cd\u91cd\u8981\u751f\u7269\u6d3b\u6027\u5206\u5b50(\u5f62\u5f0f)\u5408\u6210\u3002\u673a\u7406\u7814\u7a76\u8868\u660e\uff0c\u53cc\u94d1-\u94af\u53cc\u91d1\u5c5e\u63a5\u529b\u50ac\u5316\u5728\u53cd\u5e94\u4e2d\u53d1\u6325\u5173\u952e\u7684\u4f5c\u7528\uff0c\u6d89\u53ca\u5c06\u5361\u5bbe\u63d2\u5165X-H\u952e\u4e0e\u53cc\u91cd\u70ef\u4e19\u57fa\u53d6\u4ee3\u7684\u4e32\u8054\u8fc7\u7a0b\u3002<\/p>\n

Dirhodium\u2212Palladium Dual-Catalyzed [1 + 1 + 3] Annulation to Heterocycles Using Primary Amines or H2<\/sub>O as the Heteroatom Sources<\/p>\n

J. Xu, G. Wang, K. Ding, X. Wang, J. Am. Chem. Soc.<\/em> 2025<\/strong>, ASAP. doi: 10.1021\/jacs.4c15161<\/a>.<\/u><\/p><\/blockquote>\n

\"\"<\/p>\n

\u6b63\u6587\uff1a<\/h4>\n

\u8fd1\u5e74\u6765\uff0c\u91c7\u7528\u4e24\u79cd\u91d1\u5c5e\u50ac\u5316\u5242\u901a\u8fc7\u591a\u7ec4\u5206\u53cd\u5e94(MCRs)\u6784\u5efa\u4e24\u79cd\u65b0\u578b\u7684C-C\u4e0eC-X\u952e\uff0c\u80fd\u591f\u5feb\u901f\u6784\u5efa\u590d\u6742\u7684\u5206\u5b50\uff0c\u5e76\u5177\u6709\u663e\u8457\u7684\u539f\u5b50\u4e0e\u6b65\u9aa4\u7ecf\u6d4e\u6027\u7684\u4f18\u52bf\uff0c\u5907\u53d7\u5316\u5b66\u5bb6\u4eec\u7684\u5173\u6ce8\u3002\u5728\u6b64\u80cc\u666f\u4e0b\uff0c\u91c7\u7528\u4e00\u9505\u6cd5\u901a\u8fc7MCRs\u6709\u6548\u6784\u5efa\u6742\u73af\u5316\u5408\u7269\u5177\u6709\u91cd\u8981\u610f\u4e49\uff0c\u7279\u522b\u662f\u91c7\u7528\u7b80\u5355\u7684\u6742\u539f\u5b50\u6e90(\u5982\u4e00\u7ea7\u80fa\u6216H2<\/sub>O)\u5f15\u5165\u5173\u952e\u6742\u539f\u5b50(Scheme 1a)\u3002\u5176\u4e2d\uff0c\u901a\u8fc7\u91d1\u5c5e\u5361\u5bbe\u50ac\u5316\u91cd\u6c2e\u5316\u5408\u7269\u7684MCRs\u662f\u83b7\u5f97\u6742\u73af\u5316\u5408\u7269\u7684\u6709\u6548\u7b56\u7565\u3002\u5c3d\u7ba1\u91d1\u5c5e\u5361\u5bbe\u7684X-H(\u80fa\u6216H2<\/sub>O)\u63d2\u5165\u662f\u751f\u6210\u65b0\u578bC-X\u952e\u7684\u6709\u6548\u7b56\u7565[1]<\/sup>\uff0c\u4f46\u6d89\u53ca\u5361\u5bbe\u7684X\u2212H\u63d2\u5165\u4e0e\u73af\u5316\u6784\u5efa\u6742\u73af\u5316\u5408\u7269\u7684MCRs\u65b9\u6cd5\uff0c\u4ecd\u6709\u5f85\u8fdb\u4e00\u6b65\u7684\u63a2\u7d22[2]<\/sup>\u3002\u738b\u6653\u660e\u56e2\u961f\u8bbe\u60f3\uff0c\u901a\u8fc7Rh(II)-\u50ac\u5316\u4e00\u7ea7\u80fa\u6216H2<\/sub>O\u7684\u5361\u5bbe\u63d2\u5165\u4ee5\u53caPd-\u50ac\u5316\u53cc\u70ef\u4e19\u57fa\u53d6\u4ee3\u7684\u53cc\u91d1\u5c5e\u50ac\u5316\u4f53\u7cfb\uff0c\u53ef\u5b9e\u73b0\u6742\u73af\u5316\u5408\u7269\u7684\u5408\u6210[3]<\/sup>(Scheme 1b,c)\u3002\u7136\u800c\uff0c\u8be5\u7b56\u7565\u5b58\u5728\u4e00\u5b9a\u7684\u6311\u6218\uff0c\u5982\u91d1\u5c5e\u50ac\u5316\u5242\u4e4b\u95f4\u517c\u5bb9\u6027\u3001\u673a\u7406\u7684\u590d\u6742\u6027\u3001\u52a8\u529b\u5b66\u7684\u5e73\u8861\u4ee5\u53ca\u53cd\u5e94\u7684\u7ade\u4e89\u6027\u7b49\u6f5c\u5728\u7684\u95ee\u9898\u3002\u8fd9\u91cc\uff0c\u4e2d\u56fd\u79d1\u5b66\u9662\u4e0a\u6d77\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\u738b\u6653\u660e\u8bfe\u9898\u7ec4\u62a5\u9053\u4e00\u79cd\u53cc\u94d1-\u94af\u53cc\u91cd\u50ac\u5316\u03b1<\/em>-\u91cd\u6c2e\u916f\u884d\u751f\u7269\u3001\u70ef\u4e19\u57fa\u4e8c\u4e59\u9178\u916f\u4e0e\u82ef\u80fa(\u6216H2<\/sub>O)\u7684\u4e09\u7ec4\u5206[1+1+ 3] \u73af\u5316\u53cd\u5e94\uff0c\u76f4\u63a5\u5408\u6210\u4e86\u4e00\u7cfb\u5217\u6709\u4ef7\u503c\u7684\u53d6\u4ee3\u5421\u54af\u70f7\u4e0e\u56db\u6c22\u544b\u5583\u884d\u751f\u7269(Scheme 1c)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u4e0a\u8ff0\u5408\u6210\u7684\u4ea7\u7269\u53ef\u4f5c\u4e3a\u51e0\u79cd\u91cd\u8981\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u5173\u952e\u5408\u6210\u524d\u4f53(Scheme 1b)\u3002\"\"<\/p>\n

\u9996\u5148\uff0c\u4f5c\u8005\u91c7\u7528\u82ef\u80fa(1a<\/strong>)\u3001\u03b1<\/em>-\u91cd\u6c2e\u916f\u884d\u751f\u7269(2a<\/strong>)\u4e0e2-\u4e9a\u7532\u57fa\u4e19\u70f7-1,3-\u4e8c\u4e59\u9170\u6c27\u57fa(3a<\/strong>)\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\uff0c\u8fdb\u884c\u76f8\u5173\u53cd\u5e94\u6761\u4ef6\u7684\u4f18\u5316\u7b5b\u9009 (Table 1)\u3002\u8fdb\u800c\u786e\u5b9a\u6700\u4f73\u7684\u53cd\u5e94\u6761\u4ef6\u4e3a\uff1a\u91c7\u7528Rh2<\/sub>(Oct)4<\/sub>\u4e0ePd(OAc)2<\/sub>\u4f5c\u4e3a\u91d1\u5c5e\u50ac\u5316\u5242\uff0cBINAP\u4f5c\u4e3a\u914d\u4f53\uff0cK2<\/sub>CO3<\/sub>\u4f5c\u4e3a\u78b1\uff0c\u5728MeCN\u53cd\u5e94\u6eb6\u5242\u4e2d\uff0c\u53cd\u5e94\u6e29\u5ea6\u4e3a90 o<\/sup>C\uff0c\u6700\u7ec8\u83b7\u5f9787%\u6536\u7387\u7684\u4ea7\u72694a<\/strong>\u3002\"\"<\/p>\n

\u5728\u4e0a\u8ff0\u7684\u6700\u4f73\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u4f5c\u8005\u91c7\u7528\u80fa\u4f5c\u4e3a\u6742\u539f\u5b50\u6e90\uff0c\u5bf9\u53cd\u5e94\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u6df1\u5165\u7814\u7a76(Scheme 2)\u3002\u9996\u5148\uff0c\u542b\u6709\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u7684\u82ef\u80fa\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694a<\/strong>–4p<\/strong>\uff0c\u6536\u7387\u4e3a53-95%\u3002\u8418\u80fa\u3001\u5421\u5576\u80fa\u4ee5\u53caBocNH2<\/sub>\uff0c\u4e5f\u662f\u5408\u9002\u7684\u5e95\u7269\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694q<\/strong>–4s<\/strong>\uff0c\u6536\u7387\u4e3a54-75%\u3002\u7136\u800c\uff0c\u5728\u6807\u51c6\u53cd\u5e94\u6761\u4ef6\u4e0b\uff0c\u70f7\u57fa\u80fa\u3001\u5bf9\u7532\u82ef\u78fa\u9170\u80fa\u4e0e\u4e59\u9170\u80fa\uff0c\u672a\u80fd\u6709\u6548\u7684\u53cd\u5e94(Scheme 2a)\u3002\u5176\u6b21\uff0c\u5f53\u91cd\u6c2e\u5316\u5408\u7269\u4e2d\u542b\u6709\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u82b3\u57fa\u4e0e\u567b\u5429\u57fa\u65f6\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694t<\/strong>–4ah<\/strong>\uff0c\u6536\u7387\u4e3a50-97%\u3002\u5f53\u5c06\u91cd\u6c2e\u5316\u5408\u7269\u7684\u7532\u916f\u5206\u522b\u6539\u4e3a\u4e59\u916f\u3001\u53d4\u4e01\u916f\u3001\u82c4\u57fa\u916f\u6216\u4e8c\u82ef\u7532\u57fa\u916f\uff0c\u53cd\u5e94\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694ai<\/strong>–4al<\/strong>\uff0c\u6536\u7387\u4e3a61-96%\u3002\u540c\u65f6\uff0c1a<\/strong>\u30013a<\/strong>\u4e0e\u91cd\u6c2e\u82b3\u57fa\u916f\u6216\u82c4\u57fa\u7532\u57fa\u916e\u884d\u751f\u7684\u91cd\u6c2e\u5316\u5408\u7269\uff0c\u4e5f\u53ef\u4ee5\u987a\u5229\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694am<\/strong>(\u6536\u7387\u4e3a75%)\u4e0e4an<\/strong>(\u6536\u7387\u4e3a94%)\u30023a<\/strong>\u30011p<\/strong>\u4e0e2am<\/strong>\u7684\u53cd\u5e94\uff0c\u4e5f\u53ef\u4ee576%\u7684\u6536\u7387\u5f97\u5230\u6240\u9700\u4ea7\u72694ao<\/strong>(Scheme 2b)\u3002\u6b64\u5916\uff0c1,3-\u4e8c\u6c2f-2-\u4e9a\u7532\u57fa\u4e19\u70f7(3b<\/strong>)\u4e0e\u70ef\u4e19\u57fa\u4e8c\u9187\u4e8c\u916f(3c<\/strong>\u4e0e3d<\/strong>)\uff0c\u4e5f\u80fd\u591f\u4e0e1a<\/strong>\u4e0e2a<\/strong>\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694a<\/strong>\uff0c\u6536\u7387\u4e3a50-82%\u3002\u7136\u800c\uff0c\u7136\u800c\uff0c\u672b\u7aef\u53d6\u4ee3\u7684\u82ef\u57fa\u70ef\u4e19\u57fa\u4e8c\u4e59\u9178\u916f(3e<\/strong>)\uff0c\u4ec5\u83b7\u5f97\u5fae\u91cf\u7684\u4ea7\u7269\uff0c\u53ef\u80fd\u662f\u7a7a\u95f4\u4f4d\u963b\u5bfc\u81f4(Scheme 2c)\u3002\u503c\u5f97\u6ce8\u610f\u7684\u662f\uff0c\u8be5\u7b56\u7565\u8fd8\u53ef\u7528\u4e8e\u4e00\u4e9b\u751f\u7269\u6d3b\u6027\u5206\u5b50\u7684\u540e\u671f\u884d\u751f\u5316\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72694ap<\/strong>–4aw<\/strong>\uff0c\u6536\u7387\u4e3a64-92% (Scheme 2d)\u3002\"\"<\/p>\n

\u968f\u540e\uff0c\u901a\u8fc7\u5bf9\u53cd\u5e94\u6761\u4ef6\u7684\u518d\u6b21\u4f18\u5316\u540e\u53d1\u73b0\uff0c\u6c34\u4e5f\u53ef\u4ee5\u4f5c\u4e3a\u6742\u539f\u5b50\u6e90\u3002\u56e0\u6b64\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u5e95\u7269\u8303\u56f4\u8fdb\u884c\u4e86\u6df1\u5165\u7814\u7a76(Scheme 3)\u3002\u9996\u5148\uff0c\u5f53\u91cd\u6c2e\u5316\u5408\u7269\u4e2d\u542b\u6709\u4e0d\u540c\u7535\u6027\u53d6\u4ee3\u82b3\u57fa\u4e0e\u567b\u5429\u57fa\u65f6\uff0c\u5747\u53ef\u987a\u5229\u8fdb\u884c\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72695a<\/strong>–5l<\/strong>\uff0c\u6536\u7387\u4e3a40-67%\u3002\u5176\u6b21\uff0c\u5f53\u5c06\u91cd\u6c2e\u5316\u5408\u7269\u7684\u7532\u916f\u5206\u522b\u6539\u4e3a\u4e59\u916f\u4e0e\u82c4\u57fa\u916f\u65f6\uff0c\u53cd\u5e94\u4e5f\u80fd\u591f\u987a\u5229\u8fdb\u884c\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72695m<\/strong>(\u6536\u7387\u4e3a66%)\u4e0e5n<\/strong>(\u6536\u7387\u4e3a40%)\u3002\u6b64\u5916\uff0c\u542b\u6709\u82b3\u57fa\u03b1<\/em>-\u91cd\u6c2e\u916f\u7684\u751f\u7269\u6d3b\u6027\u5206\u5b50\uff0c\u4e5f\u4e0e\u4f53\u7cfb\u517c\u5bb9\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u4ea7\u72695o<\/strong>–5r<\/strong>\uff0c\u6536\u7387\u4e3a51-72%\u3002\"\"<\/p>\n

\u4e4b\u540e\uff0c\u4f5c\u8005\u5bf9\u53cd\u5e94\u7684\u5b9e\u7528\u6027\u8fdb\u884c\u4e86\u7814\u7a76(Scheme 4)\u3002\u9996\u5148\uff0c\u514b\u7ea7\u89c4\u6a21\u5b9e\u9a8c\uff0c\u540c\u6837\u53ef\u4ee583%\u7684\u6536\u7387\u5f97\u5230\u4ea7\u72694a<\/strong>\u3002\u540c\u65f6\uff0c4a<\/strong>\u8fd8\u53ef\u8fdb\u884c\u591a\u79cd\u884d\u751f\u5316\uff0c\u5982\u8fd8\u539f\u3001\u73af\u4e19\u70f7\u5316\u3001\u4ea4\u53c9\u590d\u5206\u89e3\u7b49\u53cd\u5e94\uff0c\u83b7\u5f97\u76f8\u5e94\u7684\u884d\u751f\u72696<\/strong>–9<\/strong>\uff0c\u6536\u7387\u4e3a46-92%(Scheme 4a)\u3002\u5176\u6b21\uff0c\u4e0a\u8ff0\u5408\u6210\u7684\u4ea7\u7269\uff0c\u901a\u8fc7\u4e00\u7cfb\u5217\u4e0d\u540c\u7684\u53cd\u5e94\uff0c\u8fd8\u53ef\u5236\u5907\u51e0\u79cd\u751f\u7269\u6d3b\u6027\u5206\u5b50\uff0c\u5982KSP\u6291\u5236\u5242\u7684\u524d\u4f53(13<\/strong>)\u3001\u6297\u771f\u83cc\u836f\u7269\u6cca\u6c99\u5eb7\u5511\u7684\u6838\u5fc3\u9aa8\u67b6(16<\/strong>)\u3001\u03b1<\/em>-\u4e9a\u7532\u57fa-\u03b3<\/em>-\u4e01\u5185\u916f(19<\/strong>)\u4e0e\u8d8b\u5316\u56e0\u5b50\u53d7\u4f53\u6d3b\u6027\u7684\u8c03\u8282\u5242(22<\/strong>)(Schemes 4b-4e)\"\"<\/p>\n

\u6700\u540e\uff0c\u4f5c\u8005\u5bf9\u4e0a\u8ff0\u73af\u5316\u8fc7\u7a0b\u7684\u53cd\u5e94\u673a\u7406\u8fdb\u884c\u8fdb\u4e00\u6b65\u7814\u7a76(Scheme 5)\u3002\u9996\u5148\uff0c1a<\/strong>\u30012a<\/strong>\u4e0e3a<\/strong>\u7684\u53cd\u5e94\u52a8\u529b\u5b66\u66f2\u7ebf\u8868\u660e\uff0c\u5361\u5bbe\u63d2\u5165\u4ea7\u726923a<\/strong>\u5728\u524d30\u5206\u949f\u5185\u4ea7\u751f\u5e76\u8fdb\u4e00\u6b65\u8f6c\u5316\u4e3a\u6700\u7ec8\u4ea7\u72694a<\/strong>\u3002\u540c\u65f6\uff0c\u50ac\u5316\u6700\u6709\u53ef\u80fd\u4ee5\u4e32\u8054\u65b9\u5f0f\u8fdb\u884c\uff0c23a<\/strong>\u5145\u5f531a<\/strong>\u4e0e2a<\/strong>\u53cd\u5e94\u539f\u4f4d\u4ea7\u751f\u7684\u4eb2\u6838\u8bd5\u5242\u3002\u5bf9\u7167\u5b9e\u9a8c\u8868\u660e\uff0c\u6bcf\u79cd\u7ec4\u5206\u5728\u8fd9\u79cd\u53cc\u91cd\u50ac\u5316\u4e2d\u7684\u91cd\u8981\u6027\u3002Rh(II)2<\/sub>\u5f88\u53ef\u80fd\u901a\u8fc7\u7c7b\u5361\u5bbe\u914d\u5408\u7269N-H\u63d2\u5165\u53cd\u5e94\u4ece\u800c\u751f\u6210\u4e2d\u95f4\u4f5323a<\/strong>\uff0c\u800cPd(OAc)2<\/sub>\/BINAP\u4ea7\u751f\u7684Pd\u914d\u5408\u7269\u5c06\u50ac\u5316\u540e\u7eed\u7684\u70ef\u4e19\u57fa\u53d6\u4ee3\u53cd\u5e94(Scheme 5A)\u3002<\/p>\n

\u5176\u6b21\uff0cH2<\/sub>O\u30012a<\/strong>\u4e0e3a<\/strong>\u7684\u53cd\u5e94\u52a8\u529b\u5b66\u66f2\u7ebf\u8868\u660e\uff0c\u5316\u5408\u726924a<\/strong>\u7684\u6d53\u5ea6\u5728\u524d10\u5206\u949f\u5185\u589e\u52a0\uff0c\u7136\u540e\u901a\u8fc7\u8fdb\u4e00\u6b65\u8f6c\u5316\u4e3a\u6700\u7ec8\u4ea7\u72695a<\/strong>\u800c\u9010\u6e10\u964d\u4f4e\u3002\u540c\u65f6\uff0c\u5361\u5bbe\u8bf1\u5bfc\u7684O-H\u952e\u63d2\u5165\u4e0e\u968f\u540e\u7684\u4e8c\u70ef\u4e19\u57fa\u5316\u662f\u4e00\u4e2a\u63a5\u529b\u50ac\u5316\u7684\u8fc7\u7a0b\u3002\u5bf9\u7167\u5b9e\u9a8c\u8fdb\u4e00\u6b65\u8868\u660e\u4e86\u6bcf\u79cd\u7ec4\u5206\u5728\u8fd9\u79cd\u53cc\u91cd\u50ac\u5316\u4e2d\u7684\u91cd\u8981\u6027(Scheme 5B)\u3002<\/p>\n

\u6b64\u5916\uff0c\u9010\u6b65\u5b9e\u9a8c\u7ed3\u679c\u8868\u660e\uff0c23a<\/strong>\u53ef\u80fd\u662f\u8be5\u8fc7\u7a0b\u4e2d\u7684\u4e2d\u95f4\u4f53(Scheme 5C)\u3002\u540c\u65f6\uff0c23a<\/strong>\u4e0e\u70ef\u4e19\u57fa\u4e8c\u4e59\u9178\u916f3a<\/strong>\u7684\u5206\u5b50\u95f4N<\/em>-\u70ef\u4e19\u57fa\u5316\u4ee5\u53ca\u968f\u540e\u7684\u5206\u5b50\u5185\u70ef\u4e19\u57fa\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u53ef\u83b7\u5f97\u73af\u5316\u4ea7\u72694a<\/strong>(Scheme 5C)\u3002<\/p>\n

\u57fa\u4e8e\u4e0a\u8ff0\u7684\u5b9e\u9a8c\u7814\u7a76\uff0c\u4f5c\u8005\u63d0\u51fa\u5982\u4e0b\u5408\u7406\u7684\u53cd\u5e94\u673a\u7406(Scheme 5D)\u3002\u9996\u5148\uff0c2a<\/strong>\u4e0e[Rh(II)2<\/sub>]\u53cd\u5e94\u539f\u4f4d\u751f\u6210Rh(II)-\u7c7b\u5361\u5bbeA<\/strong>\u3002\u5176\u6b21\uff0c\u82ef\u80fa(1a<\/strong>)\u6355\u83b7\u7c7b\u5361\u5bbeA<\/strong>\uff0c\u751f\u6210\u94f5\u53f6\u7acb\u5fb7\u4e2d\u95f4\u4f53B\uff0c\u5176\u901a\u8fc7[1,2]-\u8d28\u5b50\u8f6c\u79fb\u8fdb\u4e00\u6b65\u8f6c\u5316\u4e3aN-H\u63d2\u5165\u4ea7\u726923a<\/strong>\u3002\u5728\u63a5\u529b\u50ac\u5316\u9014\u5f84\u4e2d\uff0c\u70ef\u4e19\u57fa\u4e8c\u4e59\u9178\u916f(3a<\/strong>)\u5728\u94af(0)\u4e0a\u53d1\u751f\u6c27\u5316\u52a0\u6210\u53cd\u5e94\uff0c\u91ca\u653e\u51fa\u4e59\u9178\u6839\u9634\u79bb\u5b50\uff0c\u5e76\u751f\u6210\u03c0<\/em>-\u70ef\u4e19\u57fa\u94af\u4e2d\u95f4\u4f53C<\/strong>\u3002\u7136\u540e\uff0c\u4e2d\u95f4\u4f53C<\/strong>\u4e0eN-H\u63d2\u5165\u4ea7\u726923a<\/strong>\u53d1\u751fN<\/em>-\u70ef\u4e19\u57fa\u5316\u53cd\u5e94\uff0c\u751f\u6210\u4e2d\u95f4\u4f53D<\/strong>\u3002\u5728\u78b1\u4e0ePd(0)\u5b58\u5728\u4e0b\uff0c\u70ef\u4e19\u57faPd\u4e2d\u95f4\u4f53E<\/strong>\u901a\u8fc7\u7b2c\u4e8c\u6b21\u6c27\u5316\u52a0\u6210\u53cd\u5e94\u751f\u6210\u3002\u6700\u540e\uff0c\u901a\u8fc7\u5206\u5b50\u5185\u70ef\u4e19\u57fa\u70f7\u57fa\u5316\u53cd\u5e94\uff0c\u4ece\u800c\u751f\u6210\u76ee\u6807\u4ea7\u72694a<\/strong>\uff0c\u5e76\u518d\u751fPd(0)\u50ac\u5316\u5242\u3002\"\"<\/p>\n

\u603b\u7ed3\uff1a<\/h4>\n

\u4e2d\u56fd\u79d1\u5b66\u9662\u4e0a\u6d77\u6709\u673a\u5316\u5b66\u7814\u7a76\u6240\u738b\u6653\u660e\u8bfe\u9898\u7ec4\u5f00\u53d1\u4e86\u4e00\u79cd\u53cc\u94d1(II)\/\u94af(0)\u53cc\u91cd\u50ac\u5316\u4e09\u7ec4\u5206[1+1+3]\u73af\u5316\u53cd\u5e94\uff0c\u91c7\u7528\u82ef\u80fa\u6216\u6c34\u3001\u91cd\u6c2e\u5316\u5408\u7269\u4e0e\u70ef\u4e19\u57fa\u4e8c\u4e59\u9178\u916f\u4e3a\u5e95\u7269\uff0c\u53ef\u5feb\u901f\u6784\u5efa3-\u4e9a\u7532\u57fa\u5421\u54af\u70f7\u4e0e3-\u4e9a\u7532\u57fa\u56db\u6c22\u544b\u5583\u884d\u751f\u7269\u3002\u540c\u65f6\uff0c\u8be5\u7b56\u7565\u5177\u6709\u9ad8\u5ea6\u7684\u5b98\u80fd\u56e2\u8010\u53d7\u6027\uff0c\u5e76\u53ef\u7528\u4e8e\u751f\u7269\u6d3b\u6027\u5929\u7136\u4ea7\u7269\u4e0e\u836f\u7269\u5316\u5408\u7269\u7684\u540e\u671f\u884d\u751f\u5316\u4ee5\u53ca\u751f\u7269\u6d3b\u6027\u5316\u5408\u7269\u7684\u7b80\u6613\u5408\u6210\u3002<\/p>\n

\u53c2\u8003\u6587\u732e\uff1a<\/strong><\/h4>\n