IRIDIUM COMPLEXES OF MOLECULAR NITROGEN
IRIDIUM COMPLEXES OF MOLECULAR NITROGEN
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DOI：
10.1021/ja01022a018
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发表时间：
1968-01-01
影响因子：
15
通讯作者：
KANG, JW
中科院分区：
文献类型：
--
作者：
COLLMAN, JP;KUBOTA, M;KANG, JW
iraĞ 的反应。 s-氯羰基双（三苯基膦）铱 (I) 与有机叠氮化物生成分子氮、3 和有机异氰酸酯的稳定络合物。光谱和动力学证据支持图 1 中描述的机制。已经检查了改变叠氮化物、中心金属和辅助配体的特性对反应速率的影响。这些结果表明，在与氧化加成相关的反应中，叠氮化物充当亲电子试剂，金属充当碱。氮络合物3形成更高配位的烯烃衍生物9，但CO、三苯基膦和酰基异氰酸酯取代氮。 3、9 和先前描述的配合物中配位氮的红外吸收带根据 dT-p、背键进行讨论。
Reaction of íraĞ. s-chlorocarbonylbis (triphenylphosphine) iridium (I) with organic azides yields a stable complex of molecular nitrogen, 3, andorganic isocyanates. Spectral and kinetic evidence supports the mechanism depicted in Figure 1. The effects of changing the character of the azide, the central metal, and the ancillary ligands on the reaction rate have been examined. These results suggest that the azide functions as an electrophile and the metal as a base in a reaction related to oxidative addition. The nitrogen complex 3 forms a higher coordinate ole-fin derivative 9, but CO, triphenylphosphine, and acylisocyanates displace nitrogen. The infrared absorption bands of coordinated nitrogen in 3, 9, and previously described complexes are discussed in terms of dT-p, back-bonding.