Bond Formation and Coupling between Germyl and Bridging Germylene Ligands in Dinuclear Pd(I) Complexes
Bond Formation and Coupling between Germyl and Bridging Germylene Ligands in Dinuclear Pd(I) Complexes
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双核 Pd(I) 配合物中甲锗烷基和桥甲甲甲亚基配体之间的键形成和偶联
DOI：
10.1002/anie.201411041
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Susumu Kawauchi
中科院分区：
文献类型：
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作者：
Makoto Tanabe;Shumpei Omine;Naoko Ishikawa;Kohtaro Osakada;Yoshihiro Hayashi;Susumu Kawauchi
双核钯（I）配合物[L（Ar 2 HGe）Pd（μ-GeAr 2）2 Pd（GeHAr 2）L]（Ar=Ph，p-Tol; L= PMe 3，tBuNC）含有末端甲锗基和桥连甲锗基配体，实验观察到的Ge Ge键长为2.8263（4）<$（L= PMe 3）和2.928（1）<$（L=tBuNC），接近迄今报道的最长Ge Ge键[2.714（1）<$]。 通过DFT计算、Wiberg键指数（WBI）和自然键轨道（NBO）分析，证实了锗烯基和锗烷基配体之间存在着显著的Ge相互作用（PMe 3络合物> tBuNC络合物）.将tBuNC交换为PMe 3配体增加了Ge-CN-Ge相互作用，并同时激活了两个Pd-Ge键。将螯合的双膦1，2-双（二乙基膦基）乙烷（depe）加入到PMe 3复合物中，导致甲锗烷基和甲锗烯配体的分子内偶联，然后挤出二锗烷。
The dinuclear palladium(I) complexes [L(Ar2HGe)Pd(μ‐GeAr2)2Pd(GeHAr2)L] (Ar=Ph, p‐Tol; L=PMe3, tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge⋅⋅⋅Ge bond lengths of 2.8263(4) Å (L=PMe3) and 2.928(1) Å (L=tBuNC), which are close to the longest GeGe bond reported to date [2.714(1) Å]. Significant Ge⋅⋅⋅Ge interactions between the germylene and germyl ligands (PMe3complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe3ligands increases the Ge⋅⋅⋅Ge interaction, and simultaneously activates two PdGe bonds. Adding the chelating diphosphine 1,2‐bis(diethylphosphino)ethane (depe) to the PMe3complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.