Nickel thioether chemistry: synthesis, structures and electrochemistry of five-co-ordinate nickel(<scp>II</scp>) complexes of [9]aneS<sub>3</sub>. Crystal structures of [Ni([9]aneS<sub>3</sub>)-(dppm)][PF<sub>6</sub>]<sub>2′</sub>, [Ni([9]aneS<sub>3</sub>)(dcpe)][PF<sub>6</sub>]<sub>2</sub>·1.25MeCN and [Ni([9]aneS<sub>3</sub>)(tdpme)][PF<sub>6</sub>]<sub>2</sub>{[9]aneS<sub>3</sub>= 1,4,7-Trithiacyclononane, dppm = Ph<sub>2</sub>PCH<sub>2</sub>PPh<sub>2′</sub>, dcpe =(C<sub>6</sub>H<sub>11</sub>)<sub>2–</sub>PC<sub>2</sub>H<sub>4</sub>P(C<sub>6</sub>H<sub>11</sub>)<sub>2′</sub>, tdpme = CH<sub>3</sub>C(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>}
作者:Alexander J. Blake、Robert O. Gould、Malcolm A. Halcrow、Martin Schröder
DOI:10.1039/dt9930002909
日期:——
[Ni([9]aneS3)(dppm)][PF6]2 crystallises in triclinic space group P, a= 10.9748(25), b= 13.9702(20), c= 15.7688(24)Å, α= 80.071(7), β= 70.817(8), γ= 76.441(8)°, Dc= 1.374 g cm–3, Z= 2; [Ni([9]aneS3)(dcpe)][PF6]2·;1.25MeCN crystallises in triclinic space group P, a= 12.432(8), b= 13.382(4), c= 15.070(6)Å, α= 86.83(2), β= 70.47(2), γ= 77.28(2)°, Dc= 1.445 g cm–3, Z= 2; [Ni([9]aneS3)(tdpme)][PF6]2 crystallises in
[Ni(L–L)Cl 2 ] L–L = Ph 2 PCH 2 PPh 2(dppm),R 2 PCH 2 CH 2 PR 2 [R = Ph(dppe),C 6 H 11(dcpe)或Me(dmpe)],具有1摩尔当量的1的顺式-Ph 2 PCH CHPPh 2(dppv),Ph 2 PCH 2 CH 2 CH 2 PPh 2(dppp)或MeC(CH 2 PPh 2)3(tdpme)} ,4,7-三硫代环壬烷([9] aneS 3)提供了复杂的阳离子[Ni([9] aneS 3)(L–L)] 2+。[Ni([9] aneS 3)(dppm)] [PF 6 ] 2,[Ni([9] aneS 3)(dcpe)] [PF 6 ] 2 ·; 1.25MeCN和[Ni([ 9] aneS 3)(tdpme)] [PF 6 ] 2显示围绕镍(II)中心具有扭曲的方形锥体几何结构的五坐标络合物,其中[9]