Experimental and theoretical study of intramolecular exchange in Ir2Rh2(CO)(12) and Ir-4(CO)(11)(mu-SO2)

Beni Z; Guidoni L; Laurenczy G; Roethlisberger U; Roulet R

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Experimental and theoretical study of intramolecular exchange in Ir2Rh2(CO)(12) and Ir-4(CO)(11)(mu-SO2)

机译：Ir2Rh2（CO）（12）和Ir-4（CO）（11）（mu-SO2）分子内交换的实验和理论研究

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As observed by variable-temperature and -pressure C-13 NMR, intramolecular carbonyl scrambling in Ir2Rh2(CO)(12) and Ir-4(CO)(11)(mu-SO2) proceeds via a 'change of basal face' mechanism. In both cases the site exchange process has a positive activation volume suggesting that the transition states contain longer M-M distances compared to ground states of C-s symmetry. Transition state structures have been located by density functional calculations including relativistic effects. These structures contain a new symmetry plane which interchanges the indistinguishable starting and final geometries. Both transition state structures contain one significantly elongated M-M distance, bearing the bridging ligand unaffected by the site exchange. Differences in molecular volumes of ground and transition state geometries as calculated from Connolly surfaces and electron densities confirm the volume expansion in both cases. The sign of the activation volume is therefore a good criterion for distinguishing between the two main site exchange processes occurring in tetrahedral d(9) carbonyl clusters, i.e. the change of basal face process and the 'merry-go-round process, as the latter presents a negative activation volume.

机译：如通过可变温度和压力C-13 NMR所观察到的，Ir2Rh2（CO）（12）和Ir-4（CO）（11）（mu-SO2）中的分子内羰基加扰是通过“基础面的变化”机理进行的。在这两种情况下，位点交换过程的正激活量都表明，与C-s对称基态相比，过渡态包含更长的M-M距离。通过密度函数计算（包括相对论效应）可以找到过渡态结构。这些结构包含一个新的对称平面，该平面互换了无法区分的起始和最终几何形状。两种过渡态结构均包含一个明显延长的M-M距离，带有不受位置交换影响的桥联配体。由Connolly表面和电子密度计算得出的基态和过渡态几何体的分子体积差异证实了两种情况下的体积膨胀。因此，激活量的符号是区分在四面体d（9）羰基簇中发生的两个主要位点交换过程的良好标准，即基础面过程的变化和旋转木马过程，后者呈现负激活量。

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《Dalton transactions: An international journal of inorganic chemistry》 |2005年第2期|共5页
作者
Beni Z; Guidoni L; Laurenczy G; Roethlisberger U; Roulet R;
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正文语种 eng
中图分类无机化学;
关键词
FLUXIONAL BEHAVIOR; CRYSTAL-STRUCTURE; CORRELATION-ENERGY; TRANSITION-STATES; DENSITY; APPROXIMATION; DERIVATIVES; CO4(CO)12; DYNAMICS; CLUSTERS;

机译：通量行为;晶体结构;关联能;过渡态;密度;亲和力;衍生物;CO4（CO）12;动力学;簇;

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Experimental and theoretical study of intramolecular exchange in Ir2Rh2(CO)(12) and Ir-4(CO)(11)(mu-SO2)

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