Synthesis and Crystal Structures of the First Stable Mononuclear Dihydrogermyl(hydrido) Platinum(II) Complexes
Synthesis and Crystal Structures of the First Stable Mononuclear Dihydrogermyl(hydrido) Platinum(II) Complexes
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DOI：
10.1021/om800809n
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发表时间：
2009-01-26
期刊：
影响因子：
2.8
通讯作者：
Ishii, Akihiko
中科院分区：
文献类型：
--
作者：
Nakata, Norio;Fukazawa, Shun;Ishii, Akihiko
在甲苯中，用（Ph3P）(2)Pt(2) （GeH(2)Trip）与（Ph3P）(2)Pt（eta(2)- c2h4）氧化加成反应合成了首个稳定的二氢戊基（羟基）铂（II）配合物顺式-(Ph3P)(2)Pt(H)(GeH(2)Trip)(2)。在NaBH4存在下，1与（dppe）PtCl2反应生成相应的配合物（dppe）Pt(H)(GeH(2)Trip)(3)和二（germyl）铂（II）配合物（dppe）Pt(GeH(2) Trip)(2)(4)。此外，配合物2与游离的Cy2PCH2CH2PCy2在甲苯中进行配体交换反应，生成（dpe）Pt(H)(GeH(2)Trip)(5)，产率中等。配合物2-5的结构通过核磁共振、红外光谱和元素分析得以完全确定。此外，2、3和5的低温x射线晶体学显示，铂的中心具有扭曲的方平面环境，这可能是由于顺式配位膦配体和锗原子上庞大的9-三烷基的空间要求所致。此外，在60℃的甲苯中，二二苯基配合物4的热重排得到了二二苯基（氢化）配合物（dppe）Pt(H)[Ge(HTrip)GeH(2)Trip](6)，产率高，没有不可逆的还原消除四氢二苯基。
The first stable dihydrogermyl(hydrido) platinum(II) complex cis-(Ph3P)(2)Pt(H)(GeH(2)Trip) (2) was synthesized by the oxidative addition reaction of an overcrowded trihydrogermane, TripGeH(3) (1, Trip = 9-triptycyl), with (Ph3P)(2)Pt(eta(2)-C2H4) in toluene. The reaction of 1 with (dppe)PtCl2 in the presence of NaBH4 afforded the corresponding hydrido complex (dppe)Pt(H)(GeH(2)Trip) (3) together with bis(germyl) platinum(II) complex (dppe)Pt(GeH(2)TriP)(2) (4). In addition, the ligand exchange reaction of complex 2 with free Cy2PCH2CH2PCy2 in toluene resulted in the forination of (dcpe)Pt(H)(GeH(2)Trip) (5) in moderate yield. The structures of complexes 2-5 were fully determined on the basis of their NMR and IR spectra and elemental analyses. Moreover, the low-temperature X-ray crystallography of 2, 3, and 5 revealed that the platinum center has a distorted square-planar environment, probably due to the steric requirement of the cis-coordinated phosphine ligands and the bulky 9-triptycyl group on the germanium atom. Furthermore, the thermal rearrangement of bis(germyl) complex 4 in toluene at 60 degrees C gave digermyl(hydrido) complex (dppe)Pt(H)[Ge(HTrip)GeH(2)Trip] (6) in high yield without irreversible reductive elimination of tetrahydrodigermane.