In its co-ordination chemistry P(NAr)(NHAr)(Ar = C6H2But3-2,4,6)(1a) behaves either as (i) a source of its conjugate base yielding Ar[graphic ommitted]Ln(2)[MLn= AIMe2, from (AIMe3)2] and (3)(MLn= Li, from LiBun), or (ii) as a neutral hydrido-PV ligand in [[graphic ommitted])2PH}], but the arsa(III)azene (1b)[the As analogue of (1a)] undergoes facile AsâNHAr bond-scission with (AIMe3)2; whereas (1b) is obtained from 2Li(NHAr)+ AsCl3 in OEt2 at 20 °C, prolonged reflux in PhMe of the same reagents furnishes a cyclometallated product;
in (2)[1.617(4)Ã
] is intermediate between the PN and PâN bond lengths in (1a), and is significantly shorter than the 1.74(1)Ã
for
in PAr(NHAr)2[obtained from PArCl2+ 2Li(NHAr)].
在配位化学中,P(NAr)(NHAr)(Ar = C6H2But3-2,4,6)(1a)要么表现为(i) 其共轭碱的来源,产生 Ar[图示省略]Ln(2)[MLn= AIMe2,来自 (AIMe3)2]和 (3)(MLn= Li、(1a)的砷类似物]与(AIMe3)2发生简单的AsâNHAr键裂解,而(1b)[(AIMe3)2的砷类似物]与(AIMe3)2发生简单的AsâNHAr键裂解;而 (1b) 是在 20°C 时由 OEt2 中的 2Li(NHAr)+AsCl3 生成的,在 PhMe 中对相同试剂进行长时间回流可生成环金属化产物;(2)中的
[1.617(4)Ã ]中的
介于 (1a) 中的 PN 键和 PâN 键长度之间,明显短于 PAr(NHAr)2[PArCl2+ 2Li(NHAr)] 中
的 1.74(1)Ã 。