in the order M=Hg(II)>;Ag(I). An X-ray structure of the red-brown crystals of [Pt 2 o -C 6 H 4 P(Ph)(CH 2 ) 3 PPh 2 } 2 Hg(O 2 CCF 3 ) 2 ] has been determined (space group Cc2a , a =14.392(2), b =19.950(1), c =19.427(1) A, V =5577.9(9) A 3 , Z =4, R =0.038, R w =0.061). The structure shows a PtHgPt triangle with bond lengths PtPt=2.7608(7) and PtHg=2.6690(10) A.
摘要在尝试合成(dppp)Pt(C 2 H 4)(dppp = 1,3-双(
二苯基膦基)
丙烷)的过程中,Pt(I)Pt(I)二聚体Pt 2 o -C 6 H 4 P(Ph)(CH 2)3 PPh 2} 2的形成产率约为5-10%。在该二聚体中,dppp
配体与两个
磷原子配位至一个Pt中心,而
配体的苯基之一被邻位
金属化至第二个Pt中心。该Pt(I)Pt(I)二聚体与Ag(O 2 CCF 3),HgCl 2和Hg(O 2 CCF 3)2的反应导致形成Pt 2至M供体加合物[Pt 2 o -C 6 H 4 P(Ph)(CH 2)3 PPh 2} 2 Z](Z = Ag(O 2 CCF 3),HgCl 2和Hg(O 2 CCF 3)2),其中Pt
铂金键虽然减弱了,但仍然完好无损。31 p 1 H} NMR光谱显示,随着Z的电负性的增加,对于近似线性的P1PtPt'P1'单元,耦合常数1