The oxidative addition of diphenylphosphine and monophenylphosphine to the electron-rich rhenium-rhenium triple bond. The isolation and characterization of compounds that contain the four-center Re(μ-X)(μ-PR2)Re cluster (X=halide)
The oxidative addition of diphenylphosphine and monophenylphosphine to the electron-rich rhenium-rhenium triple bond. The isolation and characterization of compounds that contain the four-center Re(μ-X)(μ-PR2)Re cluster (X=halide)
复制标题
二苯基膦和单苯基膦与富电子铼-铼三键的氧化加成含有四中心 Re(μ-X)(μ-PR2)Re 簇（X=卤化物）的化合物的分离和表征。
DOI：
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发表时间：
1992
期刊：
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通讯作者：
R. Walton
中科院分区：
文献类型：
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作者：
I. Ara;P. Fanwick;R. Walton
摘要二苯基膦在Re2X4(μ-dppm)2 （X=Cl或Br； dppm=Ph2PCH2PPh2）和Re2Cl4(μ-dpam)2 （dpam=Ph2AsCH2AsPh2）的Re≡Re键上氧化生成dihenium （III）配合物Re2(μ-X)(μ-PPh2)HX3(μ-LL)2。Re2(μ-O2CCH3)X4(μ-dppm)2与Ph2PH反应制备了dppm配合物，并采用类似的方法由Re2(μ-O2CCH3)Cl4(dmpm)2制备了Re2(μ-Cl)(μ-PPh2)HCl3(μ-dmpm)2 （dmpm=Me2PCH2PMe2）。苯基膦同样与Re2X4(μ-dppm)2反应生成Re2(μ-X)(μ-PHPh)HX3(μ-dppm)2。对Re2(μ-Cl)(μ-PPh2)HCl3(μ-dppm)2的x射线晶体结构进行了测定，证实了Re2(μ-Cl)（μ-PPh2）的生物八面体结构。这个络合物在空间群中结晶
$$Rar 3$$
（No. 148）， a=21.699(3) Å， α=84.50(4)°，V=10084(5) Å3, z =6。对于5770个数据，在>3.0σ(I)范围内，对结构进行了toR=0.049 （Rw0.069）的优化。Re-Re距离为2.5918(7)Å。溴化物络合物Re2(μ-Br)(μ-PPh2)HBr3(μ-dppm)2与NOPF6氧化生成不寻常的dihenium （III， II）阳离子[Re2(μ-H)(μ-Br)[P(O)Ph2]Br2(NO)(μ-dppm)2]+，结构表征为其高透酸盐[Re2(μ-H)(μ-Br)[P(O)Ph2]Br2(NO)(μ-dppm)2]ReO4·2CH2Cl2。这个络合物在空间群中结晶
$$Par 1$$
(2), a=14.187(7) Å，b=16.419(5) Å，c=16.729(5) Å， α=98.76(2)°，β=110.11(3)°，γ=104.66(3)°，V=3414(6) Å3，Z=2。对于5736个数据，在>3.0σ(I)范围内，对结构进行了toR=0.040 （Rw=0.051）的优化。证实了磷结合[P(O)Ph2]−配体、线性亚硝基和桥接羟基配体的存在。Re-Re距离为2.6273(8)Å。
AbstractDiphenylphosphine oxidatively adds to the Re≡Re bonds of Re2X4(μ-dppm)2 (X=Cl or Br; dppm=Ph2PCH2PPh2) and Re2Cl4(μ-dpam)2 (dpam=Ph2AsCH2AsPh2) to afford the dirhenium(III) complexes Re2(μ-X)(μ-PPh2)HX3(μ-LL)2. The dppm complexes have also been prepared from the reactions of Re2(μ-O2CCH3)X4(μ-dppm)2 with Ph2PH, and a similar strategy has been used to prepare Re2(μ-Cl)(μ-PPh2)HCl3(μ-dmpm)2 (dmpm=Me2PCH2PMe2) from Re2(μ-O2CCH3)Cl4(dmpm)2. Phenylphosphine likewise reacts with Re2X4(μ-dppm)2 to give Re2(μ-X)(μ-PHPh)HX3(μ-dppm)2. An X-ray crystal structure determination on Re2(μ-Cl)(μ-PPh2)HCl3(μ-dppm)2 confirms its edge-shared bioctahedral structure. This complex crystallizes in the space group
$$Rar 3$$
(No. 148) witha=21.699(3) Å, α=84.50(4)°,V=10084(5) Å3, andZ=6. The structure was refined toR=0.049 (Rw0.069) for 5770 data withI>3.0σ(I). The Re-Re distance is 2.5918(7) Å. Oxidation of the bromide complex Re2(μ-Br)(μ-PPh2)HBr3(μ-dppm)2 with NOPF6 produces the unusual dirhenium(III, II) cation [Re2(μ-H)(μ-Br)[P(O)Ph2]Br2(NO)(μ-dppm)2]+ which has been structurally characterized as its perrhenate salt, [Re2(μ-H)(μ-Br)[P(O)Ph2]Br2(NO)(μ-dppm)2]ReO4 · 2CH2Cl2. This complex crystallizes in the space group
$$Par 1$$
(No. 2) witha=14.187(7) Å,b=16.419(5) Å,c=16.729(5) Å, α=98.76(2)°, β=110.11(3)°, γ=104.66(3)°,V=3414(6) Å3,Z=2. The structure was refined toR=0.040 (Rw=0.051) for 5736 data withI>3.0σ(I). The presence of a phosphorus-bound [P(O)Ph2]− ligand, a linear nitrosyl and a bridging hydrido ligand has been confirmed. The Re-Re distance is 2.6273(8) Å.