Coordination Behavior of sterically protected phosphaalkenes on the AuCl moiety leading to catalytic 1,6-enyne cycloisomerization
Coordination Behavior of sterically protected phosphaalkenes on the AuCl moiety leading to catalytic 1,6-enyne cycloisomerization
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DOI：
10.1002/asia.200600155
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发表时间：
2006-11-01
影响因子：
4.1
通讯作者：
Yoshifuji, Masaaki
中科院分区：
文献类型：
--
作者：
Freytag, Matthias;Ito, Shigekazu;Yoshifuji, Masaaki
用MES*取代的2，3-二甲基-1，4-二磷杂-1，3-二烯、1，2-二苯基-3，4-二膦环丁烯、2，2-二(甲硫基)-1-磷烯和3，3-二苯基-1，3-二磷叉丙烯(MES*=2，4，6-三叔丁基苯基)作为金(I)配合物的P配体。(E，E)-2，3-二甲基-1，4-二磷杂丁酸-1，3-二烯作为P2配体用于分子内Au-Au接触或不存在分子内Au-Au接触的配合物的形成，这取决于1，3-二磷杂丁酸-1，3-二烯的构象。具有刚性的S-顺式P=C-C=P骨架的1，2-二苯基-3，4-二膦环丁烯得到了相应的二价(I)配合物，其平面骨架略有扭曲，分子内Au-Au接触。对于2，2-二(甲基亚磺基)-1-磷烯，只有磷原子与金配位，硫原子几乎不与金发生分子内或分子间配位。另一方面，1，3-二磷杂丙烯作为不等价的P2配体形成相应的单、双金属(I)配合物。在没有六氟锑酸银等助催化剂的情况下，一些磷杂烯-金(I)配合物对1，6-烯炔环异构化反应表现出催化活性。
Mes*-substituted 2,3-dimethyl-1,4-diphosphabuta-1,3-diene, 1,2-diphenyl-3,4-diphosphinidenecyclobutene, 2,2-bis(methylsulfanyl)-1-phosphaethene, and 3,3-diphenyt-1,3-diphosphapropenes (Mes*=2,4,6-tri-tertbutylphenyl) were employed as P ligands of gold(I) complexes. The (E,E)-2,3-dimethyl-1,4-diphosphabuta-1,3- diene functioned as a P2 ligand for digold(I) complex formation with or without intramolecular Au-Au contact, which depends on the conformation of the 1,3-diphosphabuta-1,3-diene. The 1,2-diphenyl-3,4-diphosphinidenecyclobutene, which has a rigid s-cis P=C-C=P skeleton, afforded the corresponding digold(I) complexes with a slight distortion of the planar diphosphinidene-cyclobutene framework and intramolecular Au-Au contact. In the case of the 2,2-bis(methylsulfanyl)-1-phosphaethene, only the phosphorus atom coordinated to gold, and the sulfur atom showed almost no intra- or intermolecular coordination to gold. On the other hand, the 1,3-diphosphapropenes behaved as nonequivalent P2 ligands to afford the corresponding mono- and digold(I) complexes. Some phosphaalkene-gold(I) complexes showed catalytic activity for 1,6-enyne cycloisomerization without cocatalysts such as silver hexafluoroantimonate.