Rhodium-rhodium bond protonation in [Rh2Cl2(.mu.-CO)(Ph2PCH2PPh2)2] and the structure of an unusual oxidative-addition product, [Rh2Cl3(.mu.-H)(.mu.-CO)(Ph2PCH2PPh2)2].cntdot.H2O
Rhodium-rhodium bond protonation in [Rh2Cl2(.mu.-CO)(Ph2PCH2PPh2)2] and the structure of an unusual oxidative-addition product, [Rh2Cl3(.mu.-H)(.mu.-CO)(Ph2PCH2PPh2)2].cntdot.H2O
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[Rh2Cl2(.mu.-CO)(Ph2PCH2PPh2)2] 中铑-铑键质子化和一种不寻常的氧化加成产物 [Rh2Cl3(.mu.-H)(.mu.-CO)(Ph2PCH2PPh2) 的结构
DOI：
10.1021/ic00177a023
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发表时间：
1984
期刊：
影响因子：
--
通讯作者：
M. Cowie
中科院分区：
文献类型：
--
作者：
B. Sutherland;M. Cowie
这些产物的~（31）P ~（31）H）和~（31）H NMR谱表明，它们在NMR时间尺度上是对称的，这是由于流动过程引起的，这一过程要么是由于阴离子的解离和重新配位，要么是由于HA的可逆损失;在这两个过程中，结果都是阴离子从一个铑中心转移到另一个铑中心。HBF_4加合物中的BF_4 ~-阴离子可被THF置换，得到[Rh_2Cl_2（i-H）（i-CO）（i-CO）（i-H）_2（THF）][BF_4]，其似乎具有与HBF_4加合物类似的结构，但用THF代替BF_4 ~-与一种金属配位。HCl加合物[Rh_2Cl_3（# iH）（g-CO）（CH_3）_2]的X射线结构测定证实，氯离子与一个铑原子配位，并发生了Rh-Rh键质子化。该产物具有桥接氢化物和羰基，两个末端氯配体在一个金属上，一个在另一个金属上，以及两个相互反式的桥接双氢基团。[Rh 2Cl 3（δ iH）（δ-CO）（δ）2]在空间群/2/a中以每个络合物分子一个氢结合的结晶H2O结晶，其中a= 25.021（3）k，B= 14.697（2）k，c= 27.486（3）k，k = 107.57（1），并且Z= 8。对于227个不同的参数和5535个独特的观察反射，细化已经收敛到R= 0.052和Rw= 0.058。
31P {'H) and* H NMR spectra of these products indicate that they are symmetrical on the NMR time scale owing to fluxional processes that result either from anion dissociationand recoordination or from reversible loss of HA; in both processes the result is anion transfer from one rhodium center to the other. The BF4" anion in the HBF4 adduct can be displaced by THF to yield [Rh2Cl2 (jit-H)(# i-CO)(DPM) 2 (THF)][BF4], which it seems has a structure similar to that of the HBF4 adduct butwith THF instead of BF4" coordinated to one metal. AnX-ray structure determinationof the HC1 adduct,[Rh2Cl3 (# iH)(g-CO)(DPM) 2], confirms that the chloride ion is coordinated to one rhodium atom and that Rh-Rh bond protonation has occurred. This product has bridging hydride and carbonyl groups, two terminal chloro ligands on one metal and one on the other, and two mutually trans, bridging DPM groups.[Rh2Cl3 (# iH)(^-CO)(DPM) 2] crystallizes with one hydrogen-bound H20 of crystallization per complex molecule in the space group/2/a with a= 25.021 (3) Á, b= 14.697 (2) k, c= 27.486 (3) Á, ß= 107.57 (1), and Z= 8. Refinement has converged to R= 0.052 and Rw= 0.058 for 227 parameters varied and 5535 unique observed reflections.