Cyclometallation of 2-phenylaniline and (R)-alpha-methylbenylamine by palladium(II) acetate. X-ray molecular structure of [Pd{2-(2'-NH2C6H4)C6H4}Br(PPh(3))]
Cyclometallation of 2-phenylaniline and (R)-alpha-methylbenylamine by palladium(II) acetate. X-ray molecular structure of [Pd{2-(2'-NH2C6H4)C6H4}Br(PPh(3))]
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DOI：
10.1016/0022-328x(96)06188-8
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发表时间：
1996-09-06
影响因子：
2.3
通讯作者：
Solans, X
中科院分区：
文献类型：
--
作者：
Albert, J;Granell, J;Solans, X
醋酸钯(II)与伯胺2-苯基苯胺和(R)-α-甲基苯胺作用，然后用溴化锂处理，可制备相应的环钯二聚体[Pd(C-N)BR](2)(分别为1a和1b)。通过1与Pd-d(5)和PPh(3)反应，得到了单核化合物[Pd(C-N)Br(L)]，3(L=Py-d(5))和2(L=PPh(3))。在2的氯仿溶液中加入PPH，可在配位的和游离的PPH(3)之间快速交换。变温P-31{H-1}核磁共振表明，2a的交换是通过快速平衡[Pd(C-N)BR(PPh(3))(2)]双左向右箭头[Pd(C-N)BR(PPh(3))]+PPh(3)进行的，而d(8)平面正方络合物中的取代反应在2b的情况下涉及到通常的机理。测定了2a的X射线晶体结构。晶胞参数为a=12.182(3)，b=10.502(2)，c=9.998(2)埃，α=99.24(2)，β=94.69(2)，伽马=99.13(2)度。
The action of palladium(II) acetate on the primary amines 2-phenylaniline and (R)-alpha-methylbenzylamine and subsequent treatment with LiBr allows the preparation of the corresponding cyclopalladated dimers [Pd(C-N)Br](2) (1a and 1b respectively). Mononuclear compounds [Pd(C-N)Br(L)], 3 (L = py-d(5)) and 2 (L = PPh(3)), have been obtained by reaction of 1 with py-d(5) and PPh(3). Addition of PPh, to chloroform solutions of 2 produces a rapid exchange between coordinated and free PPh(3). P-31{H-1} NMR at variable temperature suggests that this exchange proceeds for 2a through the fast equilibrium [Pd(C-N)Br(PPh(3))(2)] double left right arrow [Pd(C-N)Br(PPh(3))] + PPh(3), while the usual mechanism in substitution reactions in d(8) planar square complexes is involved in the case of 2b. The X-ray crystal structure of 2a has been determined. 2a crystallizes in the triclinic space group P (1) over bar with a = 12.182(3), b = 10.502(2), c = 9.998(2) Angstrom, alpha = 99.24(2), beta = 94.69(2) and gamma = 99.13(2)degrees.