{"id":51097,"date":"2024-03-28T08:31:29","date_gmt":"2024-03-28T00:31:29","guid":{"rendered":"https:\/\/www.chemhui.com\/?p=51097"},"modified":"2024-03-19T10:36:20","modified_gmt":"2024-03-19T02:36:20","slug":"%e7%be%8e%e5%9b%bd%e8%8a%9d%e5%8a%a0%e5%93%a5%e5%a4%a7%e5%ad%a6%e8%91%a3%e5%b9%bf%e5%bd%ac%ef%bc%9a%e9%80%9a%e8%bf%87rh%e5%82%ac%e5%8c%96%e6%97%a0%e5%bc%a0%e5%8a%9b%e8%8a%b3%e5%9f%ba-%e8%8a%b3","status":"publish","type":"post","link":"http:\/\/www.chemhui.com\/%e7%be%8e%e5%9b%bd%e8%8a%9d%e5%8a%a0%e5%93%a5%e5%a4%a7%e5%ad%a6%e8%91%a3%e5%b9%bf%e5%bd%ac%ef%bc%9a%e9%80%9a%e8%bf%87rh%e5%82%ac%e5%8c%96%e6%97%a0%e5%bc%a0%e5%8a%9b%e8%8a%b3%e5%9f%ba-%e8%8a%b3\/","title":{"rendered":"\u7f8e\u56fd\u829d\u52a0\u54e5\u5927\u5b66\u8463\u5e7f\u5f6c\uff1a\u901a\u8fc7Rh\u50ac\u5316\u65e0\u5f20\u529b\u82b3\u57fa-\u82b3\u57fa\u952e\u8fdb\u884c\u5206\u88c2\u4ea4\u53c9\u5076\u8054"},"content":{"rendered":"

\u671f\u520a\u540d\uff1aNature Catalysis<\/p>\n

DOI: 10.1038\/s41929-024-01120-9<\/p>\n

\u56e0\u4e3a\u5316\u5b66\u952e\u7684\u60f0\u6027\uff0c\u65e0\u5f20\u529b\u82b3\u57fa\u82b3\u57fa\u952e\u7684\u529f\u80fd\u5316\u4fee\u9970\u4e00\u76f4\u662f\u6709\u673a\u5408\u6210\u4e2d\u7684\u4e00\u4e2a\u6311\u6218\u3002\u672c\u6587\u4f5c\u8005\u62a5\u9053\u4e86\u4e00\u79cd\u5206\u88c2\u4ea4\u53c9\u5076\u8054\u53cd\u5e94\uff0c\u901a\u8fc7\u5207\u5272\u5e38\u89c12,2′-\u53cc\u915a\u7684\u975e\u5f20\u529b\u82b3\u57fa-\u82b3\u57fa\u952e\uff0c\u4e0e\u4e0d\u540c\u7684\u82b3\u57fa\u7898\u5316\u7269\u8fdb\u884c\u82b3\u57fa\u5316\u3002\u8be5\u53cd\u5e94\u7531\u94d1\u7edc\u5408\u7269\u50ac\u5316\uff0c\u5e76\u7531\u53ef\u9664\u53bb\u7684\u4e9a\u78f7\u9178\u76d0\u5bfc\u5411\u57fa\u56e2\u548c\u6709\u673a\u8fd8\u539f\u5242\u5982\u56db(\u4e8c\u7532\u80fa)\u4e59\u70ef\uff08TDAE\uff09\u4fc3\u8fdb\u3002\u5b9e\u9a8c\u548cDFT\u7814\u7a76\u63ed\u793a\u4e86\u4e00\u4e2a\u53ef\u4ee5\u7531\u8def\u6613\u65af\u9178\u52a9\u50ac\u5316\u5242\u52a0\u901f\u7684\u8fd8\u539f\u6d88\u9664\u51b3\u901f\u6b65\u9aa4\u3002\u8fd9\u79cd\u8026\u5408\u65b9\u6cd5\u5728\u975e\u5bf9\u79f02,6-\u4e8c\u82b3\u57fa\u5316\u82ef\u915a\u7684\u6a21\u5757\u5316\u548c\u7b80\u5316\u5408\u6210\u4ee5\u53ca\u82ef\u57fa\u5355\u5143\u7684\u9aa8\u67b6\u63d2\u5165\u4e2d\u5f97\u5230\u4e86\u5e94\u7528\u3002<\/section>\n
<\/section>\n
\u975e\u5f20\u529b\u82b3\u57fa-\u82b3\u57fa\u952e\u662f\u6709\u673a\u5206\u5b50\u4e2d\u6700\u60f0\u6027\u7684\u5171\u4ef7\u952e\u4e4b\u4e00\u3002\u867d\u7136\u5b83\u4eec\u901a\u5e38\u5b58\u5728\u4e8e\u5404\u79cd\u5929\u7136\u548c\u5408\u6210\u539f\u6599\u4e2d\uff0c\u4f46\u4e0e\u8bb8\u591a\u5176\u4ed6\u57fa\u56e2\u4e0d\u540c\uff0c\u82b3\u57fa-\u82b3\u57fa\u952e\u5f88\u5c11\u88ab\u8ba4\u4e3a\u662f\u5b98\u80fd\u5316\u7684\u6d3b\u6027\u4f4d\u70b9\u3002\u8fd9\u4e9b\u952e\u7684\u60f0\u6027\u6027\u8d28\u4f7f\u5f97\u5b83\u4eec\u96be\u4ee5\u4e0e\u4eb2\u6838\u8bd5\u5242\u6216\u4eb2\u7535\u8bd5\u5242\u53cd\u5e94\uff0c\u5e76\u4e14\u5728\u975e\u5f20\u529b\u53cc\u82b3\u57fa\u4e2d\uff0c\u9ad8\u7684\u952e\u89e3\u79bb\u80fd(\u2265 110 kcal mol\u22121<\/sup>)\u4e0d\u80fd\u4fc3\u8fdb\u81ea\u7531\u57fa\u4ecb\u5bfc\u7684\u5b98\u80fd\u5316\u3002\u8fc4\u4eca\u4e3a\u6b62\uff0c\u975e\u5f20\u529b\u82b3\u57fa-\u82b3\u57fa\u952e\u7684\u65ad\u88c2\u662f\u5728\u6c22\u88c2\u89e3\u548c\u590d\u5206\u89e3\u53cd\u5e94\u4e2d\u5b9e\u73b0\u7684\u7136\u800c\u8fd9\u4e9b\u60f0\u6027\u5316\u5b66\u952e\u7684\u6709\u6548\u8f6c\u5316\u4ecd\u7136\u662f\u4e00\u4e2a\u91cd\u5927\u7684\u6311\u6218\u3002<\/section>\n

\"1\"<\/p>\n

<\/section>\n
\u6beb\u65e0\u7591\u95ee\uff0c\u8fc7\u6e21\u91d1\u5c5e\u50ac\u5316\u7684\u4ea4\u53c9\u5076\u8054\u4e3a\u5236\u5907\u5e7f\u6cdb\u4f7f\u7528\u7684\u53cc\u82b3\u70c3\u7ed3\u6784\u63d0\u4f9b\u4e86\u4e00\u79cd\u4e0d\u53ef\u6216\u7f3a\u7684\u65b9\u6cd5\uff0c\u53cc\u82b3\u70c3\u7ed3\u6784\u901a\u5e38\u5b58\u5728\u4e8e\u836f\u54c1\u3001\u519c\u7528\u5316\u5b66\u54c1\u548c\u6709\u673a\u6750\u6599\u7684\u6838\u5fc3\u9aa8\u67b6\u4e2d\u3002\u4f20\u7edf\u7684\u4ea4\u53c9\u5076\u8054\u901a\u5e38\u6d89\u53ca\u4e24\u4e2a\u5df2\u542b\u5b98\u80fd\u56e2\u7684\u82b3\u70c3\u5e95\u7269\uff0c\u4ee5\u7b49\u6469\u5c14\u6bd4\u76f8\u4e92\u53cd\u5e94(b<\/strong>)\u3002\u672c\u6587\u4f5c\u8005\u62a5\u9053\u4e86\u4e00\u79cd\u66ff\u4ee3\u6027\u4ea4\u53c9\u5076\u8054\u6a21\u5f0f\u7684\u53d1\u5c55\uff0c\u5728\u8fd9\u79cd\u6a21\u5f0f\u4e2d\uff0c\u4ece\u6613\u4e8e\u83b7\u5f97\u76842,2′-\u53cc\u915a\u8fdb\u884c\u884d\u751f\uff0c\u518d\u4e0e\u666e\u901a\u82b3\u57fa\u5364\u5316\u7269\u53d1\u751f\u5206\u88c2\u548c\u5076\u8054\uff0c\u4ece\u800c\u751f\u6210\u53cc\u82b3\u57fa\u4ea7\u7269\u3002\u8fd9\u79cd\u5206\u88c2\u4ea4\u53c9\u5076\u8054(SXC)\u53cd\u5e94\u662f\u901a\u8fc7Rh\u50ac\u5316\u6fc0\u6d3b\u975e\u5f20\u529b\u82b3\u57fa-\u82b3\u57fa\u952e\u5b9e\u73b0\u7684(c<\/strong>)\u3002<\/section>\n

\"2\"<\/p>\n

<\/section>\n
<\/section>\n
\u8003\u8651\u5230\u82b3\u57fa\u5364\u5316\u7269\u7684Ar-X\u952e\u901a\u5e38\u6bd4\u975e\u5f20\u529b\u82b3\u57fa-\u82b3\u57fa\u952e\u66f4\u5bb9\u6613\u88ab\u6fc0\u6d3b\uff0c\u5b9e\u73b0SXC\u7684\u5173\u952e\u6311\u6218\u662f\u5982\u4f55\u63a7\u5236\u5728\u53cd\u5e94\u7684\u6bcf\u4e2a\u9636\u6bb5\u88ab\u6fc0\u6d3b\u7684\u952e\u7684\u9009\u62e9\u6027\u3002\u4f5c\u8005\u5047\u8bbe\u5e95\u7269\u914d\u4f4d\u7684Rh(I)\u9996\u5148\u901a\u8fc7\u6c27\u5316\u52a0\u6210\u4e0eArX\u53cd\u5e94\uff0c\u7136\u540e\u7ecf\u8fc7\u53cc\u7535\u5b50\u8fd8\u539f\uff0c\u5f97\u5230\u5bcc\u7535\u5b50\u7684\u82b3\u57faRh(I)\u3002\u7531\u4e8e\u5bfc\u5411\u4f5c\u7528\uff0c\u82b3\u57faRh(I)\u53ef\u4ee5\u63d2\u51652,2′-\u53cc\u915a\u5e95\u7269\u7684\u82b3\u57fa-\u82b3\u57fa\u952e\u4e2d\u3002\u4e09\u82b3\u57faRh(III)\u4e2d\u95f4\u4f53\u7684\u8fd8\u539f\u6d88\u9664\u63d0\u4f9b\u4e86\u4e00\u4e2a\u53cc\u82b3\u57fa\u4ea7\u7269\uff0c\u5269\u4f59\u7684Rh(I)\u7269\u79cd\u901a\u8fc7\u6c27\u5316\u52a0\u6210\u4e0e\u53e6\u4e00\u4e2aArX\u53cd\u5e94\uff0c\u518d\u6b21\u751f\u6210\u76ee\u6807\u4ea7\u7269\u3002<\/section>\n
\u4e3a\u4e86\u9a8c\u8bc1\u8fd9\u4e00\u5047\u8bbe\uff0c\u4ee51b<\/strong>\u4f5c\u4e3a\u6a21\u578b\u5e95\u7269\u5f00\u59cb\u7814\u7a76\u3002\u5728\u4ed4\u7ec6\u8003\u5bdf\u4e86\u5404\u79cd\u50ac\u5316\u6761\u4ef6\u540e\uff0c\u4ee5[Rh(C2<\/sub>H4<\/sub>)2<\/sub>Cl]2<\/sub>\u4e3a\u50ac\u5316\u5242\uff0c\u91d1\u5c5e\u94df\u548c\u5df4\u8c46\u9178\u4e59\u916f\u4e3a\u52a9\u50ac\u5316\u5242\uff0cTDAE\u4e3a\u8fd8\u539f\u5242\uff0c\u5b9e\u73b0\u4e86\u671f\u671b\u7684SXC\u53cd\u5e94\u3002\u968f\u540e\u8fdb\u884c\u4e86\u4e00\u7cfb\u5217\u5bf9\u7167\u5b9e\u9a8c\u5982\u88681\u6240\u793a\u3002\u5176\u4e2d\u5bcc\u7535\u5b50-OP(i<\/sup><\/em>Pr)2<\/sub>\u7684\u4f5c\u7528\u662f\u4fc3\u8fdbRh(I)\u7684\u6c27\u5316\u52a0\u6210\uff0c\u5f53\u4f7f\u7528\u5bcc\u7535\u5b50\u6027\u4e0d\u8db3\u7684-OPPh2<\/sub>\u4e3a\u5bfc\u5411\u57fa\u56e2\u65f6\uff0c\u53cd\u5e94\u6548\u7387\u660e\u663e\u964d\u4f4e\uff08entry 12\uff09\u3002<\/section>\n

\"3\"<\/p>\n

<\/section>\n
<\/section>\n
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\"4\"<\/p>\n

<\/section>\n
\u63a5\u7740\u4f5c\u8005\u53c8\u5bf9\u53e6\u4e00\u90e8\u5206\u7684\u5076\u8054\u8bd5\u5242\u82b3\u57fa\u7898\u5316\u7269\u7684\u5e95\u7269\u666e\u9002\u6027\u8fdb\u884c\u4e86\u8003\u5bdf\u3002\u95f4\u4f4d\u548c\u90bb\u4f4d\u542b\u6709\u5438\u7535\u5b50\u6216\u7ed9\u7535\u5b50\u53d6\u4ee3\u57fa\u7684\u82b3\u57fa\u7898\u5316\u7269\u90fd\u517c\u5bb9\uff0c\u66f4\u52a0\u5bcc\u7535\u5b50\u7684\u82b3\u57fa\u7898\u5316\u7269\u901a\u5e38\u5177\u6709\u66f4\u9ad8\u7684\u4ea7\u7387\u3002\u6b64\u5916\uff0c\u7a20\u82b3\u57fa\u7898\u5316\u7269\u548c\u6742\u82b3\u57fa\u7898\u5316\u7269\u4e5f\u80fd\u826f\u597d\u7684\u53c2\u4e0e\u5230\u53cd\u5e94\u4e2d\u3002\u5176\u4e2d32d<\/strong>\uff0c33d<\/strong>\uff0c35d<\/strong>\uff0c37d<\/strong>\uff0c41d<\/strong>\u56e0\u4e3a\u5728\u8be5\u53cd\u5e94\u6761\u4ef6\u4e2d\u90e8\u5206\u5e95\u7269\u4f1a\u53d1\u751f\u5206\u89e3\u6240\u4ee5\u4ea7\u7387\u8f83\u4f4e\u3002<\/section>\n

\"5\"<\/p>\n

<\/section>\n
\u7136\u540e\u4f5c\u8005\u5bf9\u673a\u7406\u8fdb\u884c\u4e86\u7814\u7a76\u3002\u9996\u5148\u7814\u7a76\u4e86In\u6dfb\u52a0\u5242\u5bf9\u53cd\u5e94\u7684\u5f71\u54cd\uff0c\u4f5c\u8005\u901a\u8fc7\u63a7\u5236\u5b9e\u9a8c\u7684\u7ed3\u679c\u63a8\u6d4bIn\u53ef\u80fd\u5728\u6709\u82b3\u57fa\u7898\u5316\u7269\u53c2\u4e0e\u7684\u53cd\u5e94\u4e2d\u8f6c\u5316\u6210\u4e86\u5177\u6709Lewis\u9178\u6027\u7684InI3<\/sub>\uff0c\u4ece\u800c\u4fc3\u8fdb\u94d1\u50ac\u5316\u5242\u7684\u5468\u8f6c\u3002<\/section>\n

\"6\"<\/p>\n

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\u4e3a\u4e86\u66f4\u52a0\u7406\u89e3\u50ac\u5316\u5faa\u73af\u7684\u8fc7\u7a0b\uff0c\u4f5c\u8005\u8fdb\u884c\u4e86DFT\u8ba1\u7b97\u3002\u5176\u4e2dLewis\u9178InI3<\/sub>\u901a\u8fc7\u4e0eRh\u548cP\u914d\u4f4d\uff0c\u589e\u5927\u4e86P\u4e0a-i<\/sup><\/em>Pr\u548c\u53e6\u4e00\u82ef\u73af\u4e0aH\u539f\u5b50\u7684\u8ddd\u79bb\uff0c\u5927\u5927\u51cf\u5c0f\u4e86\u7a7a\u95f4\u6392\u65a5\uff0c\u964d\u4f4e\u4e86\u8fd8\u539f\u6d88\u9664\u6b65\u9aa4\u4e2d\u8fc7\u6e21\u6001\u7684\u80fd\u5792\uff08TS 3-in3\u00a0<\/strong>vs\u00a0TS\u00a03<\/strong>\uff09\u3002\u4f5c\u8005\u63a8\u6d4b\u7b2c\u4e00\u6b21\u7684C-C\u952e\u8fd8\u539f\u6d88\u9664\u6216Rh(III)\u7684\u8fd8\u539f\u662f\u53cd\u5e94\u7684\u51b3\u901f\u6b65\u3002<\/section>\n

\"7\"<\/p>\n

\"8\"<\/p>\n

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\u6700\u540e\u4f5c\u8005\u901a\u8fc7\u8be5\u53cd\u5e94\u4f53\u7cfb\u8fdb\u884c\u4e86\u5408\u6210\u5e94\u7528\u3002\u901a\u8fc7\u987a\u5e8f\u7684C-H\/C-C\u952e\u82b3\u57fa\u5316\u5f97\u5230\u4e86\u4e00\u7cfb\u5217\u4e0d\u5bf9\u79f0\u76842,6-\u4e8c\u82b3\u57fa\u82ef\u915a\u7c7b\u884d\u751f\u7269\uff08a<\/strong>\uff09\u3002\u6b64\u5916\u8fd8\u53ef\u4ee5\u901a\u8fc7\u8be5\u7b56\u7565\u4e09\u6b65\u751f\u6210\u4e00\u7cfb\u5217\u95f4\u4f4d\u4e8c\u82b3\u57fa\u5316\u7684\u916a\u6c28\u9178\u884d\u7c7b\u751f\u7269\uff08b<\/strong>\uff09\u3002<\/section>\n

\"9\"<\/p>\n

\"10\"<\/p>\n

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\"11\"\u200b<\/p>\n

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