Issue 4, 1994
From the journal:

Journal of the Chemical Society, Chemical Communications

Interconversion of CN and CNH2 ligands: electrosynthesis and X-ray crystallographic structures of trans-[W(CNH2)Cl(dppe)2] and trans-[W(CNH2)Cl(dppe)2][BF4](dppe = Ph2PCH2CH2PPh2): aminocarbyne ([triple bond, length half m-dash]C–NH2) or iminomethylenium ([double bond, length half m-dash]C[double bond, length half m-dash]NH2+) ligands?

David L. Hughes,   Saad K. Ibrahim,   Hapipah Moh'd Ali  and  Christopher J. Pickett  

Abstract

Electrochemical reduction of trans-[W(CN)Cl(dppe)2] in the prsence of phenol gives trans-[W(CNH2)Cl(dppe)2]3, which can be oxidised electrochemically or chemically to the paramagnetic cation trans-[W(CNH2)Cl(dppe)2]+4; X-ray crystallographic analyses of 3 and 4[BF4] suggest that the CNH2 group at both the 18 and 17e W-centres is best described as iminomethylenium ([double bond, length half m-dash]C[double bond, length half m-dash]NH2+); 3 and the deutero-complex trans-[W(CND2)Cl(dppe)2] reduce azobenzene with regeneration of the parent cyanide, the former giving hydrazobenzene and latter PhNDNDPh, suggesting that the CNH(D)2 complexes can behave as 2H(D) atom transfer reagents.

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Article information

DOI
https://doi.org/10.1039/C39940000425
Article type
Paper

J. Chem. Soc., Chem. Commun., 1994, 425-427

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Interconversion of CN and CNH2 ligands: electrosynthesis and X-ray crystallographic structures of trans-[W(CNH2)Cl(dppe)2] and trans-[W(CNH2)Cl(dppe)2][BF4](dppe = Ph2PCH2CH2PPh2): aminocarbyne ([triple bond, length half m-dash]C–NH2) or iminomethylenium ([double bond, length half m-dash]C[double bond, length half m-dash]NH2+) ligands?

D. L. Hughes, S. K. Ibrahim, H. M. Ali and C. J. Pickett, J. Chem. Soc., Chem. Commun., 1994, 425 DOI: 10.1039/C39940000425

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