Laboratoire de Chimie de Coordination, Institut de Chimie (UMR 7177 CNRS), Université de Strasbourg, 4 rue Blaise Pascal, CS 90032, 67081 Strasbourg, France.
Dalton Trans. 2013 Sep 14;42(34):12109-19. doi: 10.1039/c3dt50555c. Epub 2013 Apr 24.
New cationic Ag(I) complexes were prepared by reaction of AgBF4 with two thioether-functionalized bis(diphenylphosphino)amine ligands, Ph2PN(p-ArSMe)PPh2 (L1) and Ph2PN(n-PrSMe)PPh2 (L2), and compared with those obtained from the unfunctionalized ligands Ph2PN(Ph)PPh2 (L3) and Ph2PN(n-Bu)PPh2 (L4), respectively. The complex Ag3(μ3-Cl)2(μ2-L1-P,P)3 (1·BF4) contains a triangular array of Ag centres supported by three bridging L1 ligands and two triply-bridging chlorides. In contrast, ligand L2 led to the coordination polymer [{Ag2(μ3-L2,-P,P,S)2(MeCN)2}{Ag2(μ2-L2-P,P)2(MeCN)2}(BF4)4]n (2) in which the tethered thioether group connects intermolecularly a Ag2 unit to the diphosphine bridging the other Ag2 unit. With L3 and L4, two similar complexes were obtained, [Ag2(μ2-L3)(BF4)2] (3) and [Ag2(μ2-L4)(BF4)2] (4), respectively, with bridging diphosphine ligands and a BF4 anion completing the coordination sphere of the metal. Complexes 1·BF4·CH2Cl2, 2·THF, 3·3CH2Cl2 and 4 have been fully characterized, including by single crystal X-ray diffraction.
新型阳离子 Ag(I) 配合物是通过 AgBF4 与两个硫醚功能化的双（二苯基膦基）胺配体 Ph2PN(p-ArSMe)PPh2（L1）和 Ph2PN(n-PrSMe)PPh2（L2）反应制备的，并与分别由未功能化配体 Ph2PN(Ph)PPh2（L3）和 Ph2PN(n-Bu)PPh2（L4）得到的配合物进行了比较。配合物Ag3(μ3-Cl)2(μ2-L1-P,P)3（1·BF4）包含一个由三个桥连 L1 配体和两个三桥连氯化物支撑的三角形 Ag 中心阵列。相比之下，配体 L2 导致配位聚合物 [{Ag2(μ3-L2,-P,P,S)2(MeCN)2}{Ag2(μ2-L2-P,P)2(MeCN)2}(BF4)4]n（2）形成，其中连接硫醚基团将一个 Ag2 单元与另一个 Ag2 单元桥接的二膦配体连接起来。对于 L3 和 L4，也得到了两个类似的配合物[Ag2(μ2-L3)(BF4)2]（3）和[Ag2(μ2-L4)(BF4)2]（4），它们都具有桥连二膦配体和 BF4 阴离子，完成了金属的配位。配合物 1·BF4·CH2Cl2、2·THF、3·3CH2Cl2 和 4 已通过单晶 X 射线衍射进行了充分的表征。
