Structural and electronic comparison of 15- to 17-electron dichloro-complexes of molybdenum and rhenium: electrochemical behaviour and crystal structures of trans-[ReCl2(dppe)2]A (A = Cl or BF4; dppe = Ph2PCH2CH2PPh2), trans-[ReCl2(dppe)2] and [NBun4]2[trans-MoCl2(dppe)2][BF4]3
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 20,p. 3015-3023
- https://doi.org/10.1039/dt9930003015
Abstract
The molecular structures of the complexes trans-[ReCl2(dppe)2]A 1(A = Cl or BF4, dppe = Ph2PCH2CH2PPh2), trans-[ReCl2(dppe)2]2 and [NBun 4]2[trans-MoCl2(dppe)2][BF4]33 have been determined by X-ray crystallography. The metal–phosphorus and –chloride bond lengths are sensitive to the number of metal d electrons. The M–P (M = Mo or Re) distances contact by ca. 0.1 Å for each electron added. In contrast, the Re–Cl distances increase by ca. 0.1 Å upon addition of one electron (d5 to d6) but the Mo–Cl distances increase by less than 0.02 Å on addition of an electron (d3 to d4). These results are interpreted mainly in terms of π effects. Reduction of these complexes leads to cleavage of the metal–chloride bond which has been tracked by ramp-clamp voltammetry.Keywords
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