Issue 19, 2003
From the journal:

Dalton Transactions

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

Luísa M. D. R. S. Martins,ab   Elisabete C. B. A. Alegria,ab   David L. Hughes,c   João J. R. Fraústo da Silvaa  and  Armando J. L. Pombeiro*a  

* Corresponding authors

a Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
E-mail: pombeiro@ist.utl.pt

b Secção de Química Inorgânica, Departamento de Engenharia Química, Instituto Superior de Engenharia de Lisboa, R. Conselheiro Emídio Navarro, 1949-014 Lisboa, Portugal

c Biological Chemistry Department, John Innes Centre, Norwich Research Park, Colney, Norwich, UK

Abstract

The first hydride–cyanamide (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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Article information

DOI
https://doi.org/10.1039/B306368B
Article type
Paper
Submitted
11 Aug 2003
Accepted
13 Aug 2003
First published
26 Aug 2003

Dalton Trans., 2003, 3743-3750

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Syntheses and properties of hydride–cyanamide 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, 3743 DOI: 10.1039/B306368B

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