Syntheses and structures of alkyl and aryl halide complexes of the type [(PiPr(3))(2)PtH(eta(1)-XR)]BArf and analogues with Et(2)O, THF, and H-2 ligands. Halide-to-metal pi bonding in halocarbon complexes
Syntheses and structures of alkyl and aryl halide complexes of the type [(PiPr(3))(2)PtH(eta(1)-XR)]BArf and analogues with Et(2)O, THF, and H-2 ligands. Halide-to-metal pi bonding in halocarbon complexes
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DOI：
10.1021/ja961836y
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发表时间：
1996-11-27
影响因子：
15
通讯作者：
Kubas, GJ
中科院分区：
文献类型：
--
作者：
Butts, MD;Scott, BL;Kubas, GJ
Pt（PiPr（3））（3）与SO2反应生成（PiPr（3））（2）Pt（SO2）（1），产率93%。将[H（OEt（2））（2）]（BArf）-B-+（BArf = B（3，5-（CF 3）（2）C6 H3）（4））加入到乙醚中的1中，在-78 ℃下以85%的分离产率得到溶剂络合物反式-[（PiPr（3））（2）Pt（H）（OEt（2））]BArf（2）。配合物2充当Pt（eta（1）-XR）型单齿卤代烃配合物的前体。用二氯甲烷重结晶2，得到反式-[（PiPr（3））（2）Pt（H）（eta（1）-ClCH_2Cl）]BArf（3），产率80%。红外光谱表明二氯甲烷结合的存在，这是由X射线晶体学证实。2或3与碘-或溴苯的反应导致卤代芳烃络合物反式-[（PiPr（3））（2）Pt（H）（eta（1）-XPh）]BArf的分离，其中X = I（4，87%产率）或Br（5，60%产率）。这两种化合物的特征在于光谱和X射线晶体学。一个意想不到的空间相互作用4，建议由分子力学计算是显着的，是合理的卤化物到金属π键。PhI配合物4在苛刻条件下分解为桥连碘化物{trans-[（PiPr（3））（2）Pt（H）]（2）（mu-I）}BArf（6），并对其结构进行了表征。当将化合物2、3、4或5中的任一种溶解在THF中时，形成THF加合物[（PiPr（3））（2）Pt（H）（THF）]BArf（7），其以78%产率分离并且还通过X射线晶体学表征。CH 2Cl 2配合物3与H2-反应生成二氢配合物tans-[（PiPr（3））（2）Pt（H）（eta（2）-H2-）]BArf。
The reaction of Pt(PiPr(3))(3) with SO2 led to the formation of (PiPr(3))(2)Pt(SO2) (1), isolated in 93% yield. The addition of [H(OEt(2))(2)](BArf)-B-+(BArf = B(3,5-(CF3)(2)C6H3)(4)) to 1 in ether at -78 degrees C afforded the solvent complex trans-[(PiPr(3))(2)Pt(H)(OEt(2))]BArf (2) in 85% isolated yield. Complex 2 served as a precursor to monodentate halocarbon complexes of the type Pt(eta(1)-XR). The dichloromethane complex trans-[(PiPr(3))(2)Pt(H)(eta(1)-ClCH2Cl)]BArf (3) was isolated in 80% yield by the recrystallization of 2 from CH2Cl2/hexane. IR spectroscopy suggested the existence of dichloromethane binding which was confirmed by X-ray crystallography. The reaction of 2 or 3 with iodo- or bromobenzene led to the isolation of the haloarene complexes trans-[(PiPr(3))(2)Pt(H)(eta(1)-XPh)]BArf, where X = I (4, 87% yield) or Br (5, 60% yield). Both compounds were characterized spectroscopically and by X-ray crystallography. An unexpected steric interaction in 4, suggested by molecular mechanics calculations to be significant, was rationalized in terms of halide-to-metal pi bonding. The PhI complex 4 decomposed under harsh conditions to the bridging iodide compound {trans-[(PiPr(3))(2)Pt(H)](2)(mu-I)}BArf (6) which was structurally characterized. The THF adduct [(PiPr(3))(2)Pt(H)(THF)]BArf (7), isolated in 78% yield and also characterized by X-ray crystallography, was formed when any of the compounds 2, 3, 4, or 5 was dissolved in THF. The CH2Cl2 complex 3 reacted with H-2 to form the dihydrogen complex tans-[(PiPr(3))(2)Pt(H)(eta(2)-H-2)]BArf which was characterized by NMR spectroscopy.