Andrieu Jacques, Braunstein Pierre, Dusausoy Yves, Ghermani Nour Edine
Laboratoire de Chimie de Coordination, Associé au CNRS (URA 416), Université Louis Pasteur, 4 rue Blaise Pascal, F-67070 Strasbourg Cédex, France, and Laboratoire de Cristallographie et Modélisation des Matériaux Minéraux et Biologiques, Associé au CNRS (URA 809), Université Henri Poincaré Nancy 1, B.P. 239, F-54506 Vandoeuvre-les-Nancy Cédex, France.
Inorg Chem. 1996 Nov 20;35(24):7174-7180. doi: 10.1021/ic951507r.
Electrophilic attack of 1 equiv of I(2) on a PC(sp)2 carbon of the Pt(II) complex (1) afforded (2) in 90% yield. Complex 2 was subsequently deprotonated by NaOEt in ethanol to give the bis(enolato) complex (3). This alpha-phosphino, alpha-iodo enolato complex was obtained directly and quantitatively by the reaction of 1 with 1 equiv of N-iodosuccinimide (NIS). When 2 equiv of NIS was used, the symmetrical complex (4) was formed selectively. In contrast to I(2), NIS was also able to functionalize the phosphino enolate ligand of complexes to give the corresponding iodo derivatives (C N = dmba (5) or 8-mq (6)). These represent the first examples in which a phosphino enolate C-H bond has been directly functionalized, i.e. replaced by a C-X bond. Attempts to use this procedure with or with were unsuccessful. Reaction of 5 with Pd(dba)(2) in the presence of tetramethylenediamine (tmeda) or 2,2'-bipyridine (bipy) afforded (7) and (8), respectively. The solid state structures of complexes 5 and 7.CH(2)Cl(2) have been determined by single-crystal X-ray diffraction: 5 crystallizes in the monoclinic space group P2(1)/n with Z = 4 in a unit cell of dimensions a = 12.867(3) Å, b = 10.625(3) Å, c = 19.509(6) Å, and beta = 102.23(2) degrees; 7.CH(2)Cl(2) crystallizes in the monoclinic space group C2/c with Z = 8 in a unit cell of dimensions a = 35.906(3) Å, b = 13.565(3) Å, c = 15.775(2) Å, and beta = 95.099(10) degrees. Complex 7 contains two palladium(II) centers, in a square-planar environment, connected by the P-C unit of a phosphino enolate ligand which adopts an unprecedented &mgr;-eta(2)(P,C):eta(2)(P,O) bonding mode. The two coordination planes are almost orthogonal and make a dihedral angle of 88.0(2) degrees, which minimizes the steric hindrance between the ligands.
1当量I₂对Pt(II)配合物(1)的一个PC(sp)₂碳进行亲电进攻，以90%的产率得到(2)。配合物2随后在乙醇中被乙醇钠去质子化，得到双烯醇盐配合物(3)。这种α - 膦基、α - 碘代烯醇盐配合物通过1与1当量的N - 碘代琥珀酰亚胺(NIS)反应直接定量得到。当使用2当量的NIS时，选择性地形成了对称配合物(4)。与I₂不同，NIS还能够使配合物的膦基烯醇盐配体官能化，得到相应的碘代衍生物（CN = dmba (5)或8 - mq (6)）。这些代表了膦基烯醇盐C - H键首次被直接官能化的例子，即被C - X键取代。尝试将此方法用于[此处原文缺失相关内容]或[此处原文缺失相关内容]均未成功。5与Pd(dba)₂在四亚甲基二胺(tmeda)或2,2'-联吡啶(bipy)存在下反应，分别得到(7)和(8)。配合物5和7·CH₂Cl₂的固态结构已通过单晶X射线衍射确定：5以单斜空间群P2(1)/n结晶，Z = 4，晶胞尺寸为a = 12.867(3) Å，b = 10.625(3) Å，c = 19.509(6) Å，β =
