Manganese-Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)2MnSn(C6H3-2,6-Mes2)]+ (dmpe = Me2PCH2CH2PMe2, Mes=2,4,6-Trimethylphenyl)
Manganese-Tin Triple Bonds: A New Synthetic Route to the Manganese Stannylidyne Complex Cation trans-[H(dmpe)2MnSn(C6H3-2,6-Mes2)]+ (dmpe = Me2PCH2CH2PMe2, Mes=2,4,6-Trimethylphenyl)
复制标题
DOI：
10.1021/ja406290t
复制
发表时间：
2013-08-07
影响因子：
15
通讯作者：
Schnakenburg, Gregor
中科院分区：
文献类型：
--
作者：
Filippou, Alexander C.;Ghana, Priyabrata;Schnakenburg, Gregor
报道了一种利用二氢络合物的倾向消除H-2的新方法，该方法以锰锡三键为特征。18价电子二氢锰配合物[MNH-(eta(2)-H-2)(Dmpe)(2)](1)(dmpe=Me2PCH2CH2PMe2)与H-2选择性提供的有机锡(II)氯化物SnCL(C6H3-2，6-MES(2))(MES=2，4，6-三甲苯基)的反应(2)消除了氯亚锡配合物反式-[H-(Dmpe)(2)Mn=锡(Cl)(C6H3-2，6-MES(2))](2)，经Na[B(C6H3-3，5-(CF3)(2))(4)]和Li[Al(OC-(CF3)(3))(4)]定量转化为反式-[H(Dmpe)(2)MnSn-(C6H3-2，6-MES(2))]A[A=B(C6H3-3，5-(CF3)(2))(4)(3a)，Al(OC(CF3)(3))(4)(3b)]。对化合物2和3a/3b进行了充分的表征，并用单晶X射线衍射法确定了化合物2和3a的结构。配合物2的特点是迄今报道的最短的锰-锡双键，大的锰-锡-C-芳基键角，以及三方-平面配位的锡中心的长的锡-氯键。这些成键特征可以通过三键共振结构[LNM Snr]Cl的强烈贡献在价键条件下合理化，并通过对DFT最小化结构2的电子密度的自然共振理论(NRT)分析得到验证。配合物3a具有迄今报道的最短的Mn-Sn键和一个线性配位的锡原子。3a/3b络合阳离子的自然键级和电子结构的NRT分析表明，3a/3b中的络阳离子是一个高极性的Mn-Sn三键，其中离子对nrt Mn-Sn键的贡献为2.25。化合物3a发生可逆单电子还原反应，表明开壳型锡基化合物可用强还原剂进行还原。
A new approach to the first complex featuring a manganese tin triple bond that takes advantage of the propensity of dihydrogen complexes to eliminate H-2 is reported. Reaction of the 18-valence-electron manganese dihydrogen hydride complex [MnH-(eta(2)-H-2)(dmpe)(2)] (1) (dmpe = Me2PCH2CH2PMe2) with the organotin(II) chloride SnCl(C6H3-2,6-Mes(2)) (Mes = 2,4,6-trimethylphenyl) selectively afforded by H-2 elimination the chlorostannylidene complex trans-[H-(dmpe)(2)Mn = Sn(Cl)(C6H3-2,6-Mes(2))] (2), which upon treatment with Na[B(C6H3-3,5-(CF3)(2))(4)] and Li[Al(OC-(CF3)(3))(4)] was transformed quantitatively into the stannylidyne complex salts trans-[H(dmpe)(2)Mn Sn-(C6H3-2,6-Mes(2))]A [A = B(C6H3-3,5-(CF3)(2))(4) (3a), Al(OC(CF3)(3))(4) (3b)]. Complexes 2 and 3a/3b were fully characterized, and the structures of 2 and 3a were determined by single-crystal X-ray diffraction. Complex 2 features the shortest Mn-Sn double bond reported to date, a large Mn-Sn-C-aryl bond angle, and a long Sn-Cl bond of the trigonal-planar-coordinated tin center. These bonding features can be rationalized in valence-bond terms by a strong contribution of the triply bonded resonance structure [LnM SnR]Cl and were verified by a natural resonance theory (NRT) analysis of the electron density of the DFT-minimized structure of 2. Complex 3a features the shortest Mn-Sn bond reported to date and a linearly coordinated tin atom. Natural bond order and NRT analyses of the electronic structure of the complex cation in 3a/3b suggested a highly polar Mn-Sn triple bond with a 65% ionic contribution to the NRT Mn-Sn bond order of 2.25. Complex 3a undergoes reversible one-electron reduction, suggesting that open-shell stannylidyne complexes might be accessible using strong reducing agents.