Re-X bonds

The broken bonds (boldface = dissociated BDEs (boldface = recommended data reference in parentheses) Methods (reference in  

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The stability of the reduced complex depends on the ability of the X ligand to accommodate the increased electron density of the Re center. In the case of ligands that cannot easily accept electron density into a low-energy orbital the increased electron density on the Re weakens the Re X bond and can lead to loss of the X ligand. Complexes such as Re(dmb)(CO)3Cl tend to form the five-coordinate radical [Re(dmb)(CO)3] species upon reduction even in MeCN [61]. This effect is stronger in the doubly reduced species that has added an electron directly to the Re center. 

A careful study of the Re3Cl9-NH3(l) system has shown that ammonolysis occurs, and that the purple material that remains upon evaporation of the resulting reaction solution is a mixture of Re3Cl6(NH2)3(NHj)3 and NH4CI. This work has permitted a meaningful reassessment of earlier studies dealing with the reaction of Re3X9 with ammonia, and with primary and secondary amines, and their reinterpretation in terms of solvolysis of the Re—X bonds. ... 

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