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Issue 19, 2003
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Syntheses and properties of hydridecyanamide and derived hydrogen-cyanamide complexes of molybdenum(IV). Crystal structure of [MoH2(NCNH2)2(Ph2PCH2CH2PPh2)2][BF4]2

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Abstract

The first hydridecyanamide (or –cyanoguanidine) complexes of molybdenum, [MoH2(NCR)2(dppe)2][BF4]2 (R = NH21a, NMe21b, NEt21c or NC(NH2)21d; 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]22 or to the bis(cyanoimide) complex trans-[Mo(NCN)2(dppe)2] 3, via base-catalysed 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.

Graphical abstract: Syntheses and properties of hydride–cyanamide and derived hydrogen-cyanamide complexes of molybdenum(iv). Crystal structure of [MoH2(NCNH2)2(Ph2PCH2CH2PPh2)2][BF4]2

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Publication details

The article was received on 11 Aug 2003, accepted on 13 Aug 2003 and first published on 26 Aug 2003


Article type: Paper
DOI: 10.1039/B306368B
Citation: Dalton Trans., 2003,0, 3743-3750

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    Syntheses and properties of hydridecyanamide and derived hydrogen-cyanamide complexes of molybdenum(IV). Crystal structure of [MoH2(NCNH2)2(Ph2PCH2CH2PPh2)2][BF4]2

    L. M. D. R. S. Martins, E. C. B. A. Alegria, D. L. Hughes, J. J. R. Fraústo da Silva and A. J. L. Pombeiro, Dalton Trans., 2003, 0, 3743
    DOI: 10.1039/B306368B

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