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
Co-ordination chemistry of higher oxidation states. Part 41. Synthesis, spectroscopic and electrochemical studies of cationic ruthenium(III) Group 15 and 16 donor ligand complexes. Structure of trans-[Ru{C6F4(AsMe2)2-o}2Br2]BF4
作者:Neil R. Champness、William Levason、Derek Pletcher、Michael Webster
DOI:10.1039/dt9920003243
日期:——
The complexes trans-[Ru(L–L)2X2]BF4[X = Cl or Br; L–L = bidentate ligand including C6H4(PMe2)2-o, C6H4(AsMe2)2-o, C6F4(AsMe2)2-o, Me2PCH2CH2PMe2, Ph2PCH2CH2PPh2, Ph2AsCHCHAsPh2, C6H4(PPh2)2-o, C6F4(PPh2)2-o, MeSCH2CH2SMe, PhSCH2CH2SPh and PhSeCH2CH2SePh] have been prepared by nitric acid oxidation of the corresponding [Ru(L–L)2X2] in aqueous HBF4 and in other ways. The complexes have been characterised
配合物反式-[Ru(L–L)2 X 2 ] BF 4 [X = Cl或Br; L–L =双齿配体,包括C 6 H 4(PMe 2)2 - o,C 6 H 4(AsMe 2)2 - o,C 6 F 4(AsMe 2)2 - o,Me 2 PCH 2 CH 2 PMe 2,苯2 PCH 2 CH 2 PPh2,Ph 2 AsCHCHAsPh 2,C 6 H 4(PPh 2) 2 - o,C 6 F 4(PPh 2) 2 - o,MeSCH 2 CH 2 SMe,PhSCH 2 CH 2 SPh和PhSeCH 2 CH 2 SePh]具有通过在HBF 4水溶液中硝酸氧化相应的[Ru(L–L) 2 X 2 ]制备以及其他方式。通过分析,IR和UV / VIS光谱,磁测量以及通过循环伏安法建立的Ru II –Ru III氧化还原电位来表征复合物。确定了反式-[Ru C 6 F 4(AsMe 2)2
Experimental and Computational Studies of the Isomerization Reactions of Bidentate Phosphine Ligands in Triosmium Clusters: Kinetics of the Rearrangements from Bridged to Chelated Isomers and X-ray Structures of the Clusters Os<sub>3</sub>(CO)<sub>10</sub>(dppbz), 1,1-Os<sub>3</sub>(CO)<sub>10</sub>(dppbzF<sub>4</sub>), HOs<sub>3</sub>(CO)<sub>9</sub>[μ-1,2-PhP(C<sub>6</sub>H<sub>4</sub>-η<sup>1</sup>)C<sub>6</sub>H<sub>4</sub>PPh<sub>2</sub>], and HOs<sub>3</sub>(CO)<sub>9</sub>[μ-1,2-PhP(C<sub>6</sub>H<sub>4</sub>-η<sup>1</sup>)C<sub>6</sub>F<sub>4</sub>PPh<sub>2</sub>]
作者:Xue Zhang、Srikanth Kandala、Li Yang、William H. Watson、Xiaoping Wang、David A. Hrovat、Weston Thatcher Borden、Michael G. Richmond
DOI:10.1021/om100783f
日期:2011.3.14
The diphosphine ligand 1,2-bis(diphenylphosphino)benzene (dppbz) reacts with the activated cluster 1,2-Os3(CO)10(MeCN)2 (1) at room temperature to furnish a mixture of the triosmium clusters 1,2-Os3(CO)10(dppbz) (2) and 1,1-Os3(CO)10(dppbz) (3), along with a trace amount of the hydridecluster HOs3(CO)9[μ-1,2-PhP(C6H4-η1)C6H4PPh2] (4). The dppbz-bridged cluster 2 forms as the kinetically controlled