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Cyanamide has been found to be a substrate of Mo¨C and V¨Cnitrogenases ; it can be reduced by these enzymes to CH4 ,CH3NH2 , and NH3.[10] It can also be hydrolyzed by cyanamide hydratase, which is a Zn-containing enzyme.[11] These enzymatic reactions most likely involve binding of cyanamide or its bases to a metal center ; hence study of the binding and reactivity of coordi-nated cyanamide is of additional interest. The reaction of the dialkyl cyanamido complexes [(NH3)5CoIIINCN(C3)23 +and cis-or trans-[PtIICl2(NCNR)2](R= Me2,Et2,C5H 10) with NH3 to generate the corresponding guanidine com-plexes has been reported.[12, 13] Meyer and co-workers have developed a novel synthesis of OsIV=NC Nthatbears2,2¡¯ :6 ¡¯ ,2 ¡¯¡¯ -terpyridine (tpy) and 2,2¡¯ -bipyridine (bpy) ligands by direct addition of CN toOsVI N. [14] The Nb of OsIV =NC N exhibits both nucleo-philic and electrophilic reactivity. It reacts readily with vari-ous electrophiles such as H+,Et3O+,CH3I, and (CH3CO)2O; and it also reacts with PPh3 and alkenes (Scheme 1).[14¨C16] Similar reaction with electrophiles has also been reported for trans-[MoIV(NCN)2(dppe)2] (dppe = 1,2-bis(diphenylphosphino)ethane) |
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alexwang0521: ½ð±Ò+15, ·ÒëEPI+1, ¡ï¡ï¡ïºÜÓаïÖú 2012-04-27 12:14:35
alexwang0521: ½ð±Ò+15, ·ÒëEPI+1, ¡ï¡ï¡ïºÜÓаïÖú 2012-04-27 12:14:35
| ÒÑ·¢ÏÖÇè°·ÄÜ×÷ΪîâºÍV-¹ÌµªÃ¸µÄµ×ÎËüÄܱ»ÕâЩø»¹ÔΪCH4 ,CH3NH2ºÍ NH3¡£ËüͬʱҲÄܱ»Çèõ£°·Ë®ºÏø£¨Ò»ÖÖº¬Ð¿µÄø£©´ß»¯Ë®½â¡£ÕâЩø´ß»¯·´Ó¦´ó¶à¿ÉÄÜÉæ¼°Çè°·µÄ½áºÏ»òÒÔ½ðÊôÖÐÐÄΪËüµÄ»ù´¡£»Òò´Ë£¬Ñо¿Æä½áºÏºÍÅäλ·´Ó¦»îÐÔÇè°·ÊÇÎÒÃǶîÍâ¸ÐÐËȤµÄÊ¡£¶þÍé»ùÇè°·¸´ºÏÎï[(NH3)5CoIIINCN(C3)23+¼°cis-or trans-[PtIICl2(NCNR)2](R= Me2,Et2,C5H 10)ÓëNH3·´Ó¦Éú³ÉÏàÓ¦µÄëÒ¸´ºÏÎïÒÑÓб¨µÀ¡£MeyerÓëÆäͬÊÂÒѽ¨Á¢ÁËÒ»ÖÖеĺϳÉOsIV=NC µÄ·½·¨ £¬2¡¯ ,6 ¡¯ ,2 ¡¯¡¯Î»µÄÈýÁªßÁ़°2,2¡¯ -¶þßÁà¤ÅäÌåͨ¹ýÖ±½Ó½«CN¼Óµ½OsVI NÖС£The Nb of OsIV =NC N ¶¼ÏÔʾºËÜÕËáÇ×Ë®ºÍÇ׵練Ӧ»îÐÔ¡£ËüÈÝÒ×Óë¸÷ÖÖÇ×µçÊÔ¼ÁÈçH+,Et3O+,CH3I, ¼°(CH3CO)2O·´Ó¦£¬ËüÒ²ÄÜÓëÈý±½»ù좼°Ï©Ìþ£¨±í1£©¡£¾Ý±¨µÀtrans-[MoIV(NCN)2(dppe)2](dppe = 1,2 - ¶þ£¨¶þ±½»ù좣©ÒÒÍé)ÄÜÓëÇ×µçÊÔ¼Á·¢ÉúÀàËÆµÄ·´Ó¦¡£ |
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