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首页> 外文期刊>Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics >Reversible displacement of polyagostic interactions in 16e [Mn(CO)(R2PC2H4PR2)(2)](+) by H-2, N-2, and SO2. Binding and activation of eta(2)-H-2 trans to CO is nearly invariant to changes in charge and cis ligands
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Reversible displacement of polyagostic interactions in 16e [Mn(CO)(R2PC2H4PR2)(2)](+) by H-2, N-2, and SO2. Binding and activation of eta(2)-H-2 trans to CO is nearly invariant to changes in charge and cis ligands

机译：H-2，N-2和SO2在16e [Mn（CO）（R2PC2H4PR2）（2）]（+）中的多声相互作用的可逆位移。 eta（2）-H-2反式与CO的结合和激活对于电荷和顺式配体的变化几乎不变

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Electrophilic 16e [Mn(CO)(R2PC2H4PR2)(2)](+) complexes (R = Et, Ph) are synthesized by metathesis of MnBr(CO)(R2PC2H4PR2)(2) with Na or Li salts of low-coordinating baron or gallium anions (e.g., [B{C6H3(3,5-CF3)(2)}(4)](-) or [Ga(C6F5)(4)](-)). They contain weak polyagostic interactions that are reversibly displaced by H-2, N-2, and SO2 (which is a surprisingly weak ligand here). The agostic aid H-2 complexes, as well as the gallium anions including the new species [{Ga(C6F5)(3)}(2)(mu-Cl)](-), have been characterized by NMR, IR, and X-ray crystallography. The agostic Mn-H distances (e.g., 2.9 Angstrom) are much longer than those found for the single agostic interactions in Mo(CO)(diphosphine)(2) and [Mn(CO)(3)(PCy3)(2)](+). The H-H and also the Mn-H distances have been determined in the H-2 complex by T-1 measurements for both the H-2 and HD isotopomers. IR data and C-O and M-C bond lengths are used to gauge the pi-acceptor strengths of ligands trans to the CO. The agostic C-H bonds are the weakest ligands and also the weakest accepters, but the H-2 ligand is an excellent acceptor as strong as N-2 and ethylene. The variation of nu(CO) on increasing the basicity of the cis-phosphine (dppe versus depe) in trans-M(CO)(diphosphine)(2)(L) is less than expected and far less than that on increasing the charge on the complex (M = Mn+ versus Mo). The H-H bond lengths (0.87-0.90 Angstrom) and J(HD) NMR couplings (32-34 Hz) in [Mn(CO)(R2PC2H4PR2)(2)(H-2)](+) and other cationic H-2 complexes with trans-CO are strikingly similar to their neutral analogues and nearly invariant. Activation of H-H in the more electrophilic cationic systems occurs primarily via increased a donation from H-2 as compared to the more electron-rich neutral analogues where back-bonding dominates. The nature of the ligand trans to H-2 (the strong acceptor CO here) controls the H-H distance more so than all of the cis ligands combined, especially fbr cationic complexes. [References: 87]
机译：亲电性16e [Mn（CO）（R2PC2H4PR2）（2）]（+）配合物（R = Et，Ph）是通过MnBr（CO）（R2PC2H4PR2）（2）与低配位男爵的Na或Li盐复分解合成的或镓阴离子（例如[B {C6H3（3,5-CF3）（2）}（4）]（-）或[Ga（C6F5）（4）]（-））。它们包含弱的多声相互作用，可被H-2，N-2和SO2（在此是令人惊讶的弱配体）可逆地置换。辅助助剂H-2配合物以及包括新物种[{Ga（C6F5）（3）}（2）（mu-Cl）]（-）的镓阴离子已通过NMR，IR和X射线晶体学。 Mn-H的远距离（例如2.9埃）比Mo（CO）（二膦）（2）和[Mn（CO）（3）（PCy3）（2）]中的单次交互作用所发现的距离长得多。 （+）。已经通过H-1和HD同位异构体的T-1测量在H-2配合物中确定了H-H距离以及Mn-H距离。 IR数据以及CO和MC键的长度用于衡量向CO转移的配体的pi受体强度。混乱的CH键是最弱的配体，也是最弱的受体，但是H-2配体是强力的出色受体作为N-2和乙烯。 nu（CO）在反式M（CO）（二膦）（2）（L）中增加顺式膦的碱度（dppe与depe）的变化小于预期且远小于增加电荷时的变化在复合物上（M = Mn +对Mo）。 [Mn（CO）（R2PC2H4PR2）（2）（H-2）]（+）和其他阳离子H-2中的HH键长（0.87-0.90埃）和J（HD）NMR耦合（32-34 Hz）具有反式-CO的复合物极其类似于其中性类似物，并且几乎不变。与亲电性较高的中性类似物相比，在较亲电子的阳离子体系中，H-H的活化主要是通过增加H-2的捐赠来实现的。与所有顺式配体（尤其是阳离子型阳离子配合物）结合使用时，配体转化为H-2（此处为强受体CO）的性质更能控制H-H距离。 [参考：87]

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