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Advisor(s)
Abstract(s)
The first hydride–cyanamide (or –cyanoguanidine) complexes of molybdenum, [MoH2(NCR)2(dppe)2][BF4]2 (R = NH2 1a, NMe2 1b, NEt2 1c or NC(NH2)2 1d; dppe = Ph2PCH2CH2PPh2), have been prepared by treatment of [MoH4(dppe)2] in THF with the appropriate cyanamide (or cyanoguanidine) in the presence of HBF4. Reaction of 1a with a base leads to the bis(hydrogen-cyanamide) [or bis(hydrogen-cyananoimide)] complex trans-[Mo(NCNH)2(dppe)2][BF4]2 2 or to the bis(cyanoimide) complex trans-[Mo(NCN)2(dppe)2] 3, via basecatalysed or base-promoted dehydrogenation, whereas cathodically-induced dehydrogenation appears to form [MoH2(NCNH)(NCNH2)(dppe)2] 4. The spectroscopic properties of the complexes are also reported along with their electrochemical behaviours and the molecular structure of 1a as established by X-ray crystallography which indicates the presence of the NCNH2 ligands involved in two hydrogen bonds connecting the ions in dimeric units.
Description
Keywords
Hydride–cyanamide Hydrogen-cyanamide Molybdenum(IV)
Citation
MARTINS, Luísa M. D. R. S.; [et al] – Syntheses and properties of hydride–cyanamide and derived hydrogen-cyanamide complexes of molybdenum(IV). Crystal structure of [MoH2(NCNH2)2(Ph2PCH2CH2PPh2)2][BF4]2. Journal of the Chemical Society, Dalton Transactions. 2003, N.º 19 (2003), pp. 3743-3750
Publisher
Royal Society of Chemistry