Co-ordination chemistry of higher oxidation states. Part 40. Spectroscopic, electrochemical and structural studies of cationic osmium-(III) and -(IV) diphosphine and diarsine complexes
作者:Neil R. Champness、William Levason、Derek Pletcher、Mark D. Spicer、Michael Webster
DOI:10.1039/dt9920002201
日期:——
spectra of the osmium-(III) and -(IV) complexes are proposed. The X-ray structure of trans-[Oso-C6H4(AsMe2)2}2Cl2]ClO4 is reported: monoclinic, space group C2/m, a= 13.890(2), b= 10.381(2), c= 11.682(3)Å, β= 113.86(2)°, Z= 2, and with R= 0.039. Osmium LIII-edge (and where appropriate bromine K-edge) extended X-ray absorption fine structure data for the complexes trans-[Oso-C6H4(AsMe2)2}2X2]n+(n=
III(III)配合物反-[Os(L-L)2 X 2 ] BF 4 [X = Cl或Br; L–L = o -C 6 H 4(PMe 2)2,o -C 6 H 4(AsMe 2)2,o -C 6 H 4(AsMe 2)(PMe 2),o -C 6 F 4( AsMe 2)2,Ph 2 PCH 2 CH通过稀释HNO 3制备了2 PPh 2,Me 2 PCH 2 CH 2 PMe 2,Ph 2 AsCHCHAsPh 2, o -C 6 H 4(PPh 2) 2或o -C 6 F 4(PPh 2) 2 ]。在HBF 4中氧化( II)类似物。浓HNO 3可将大多数这些络合物转化为Os IV,但不稳定仅当L–L = o -C 6 H 4(PMe 2)2,o -C 6 H 4(AsMe 2)时,才分离出反式-[Os(L–L)2 X 2 ] [ClO 4 ] 2为固体。2或o -C 6 H 4(AsMe