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In the presence of stoichiometric or catalytic amounts of [M{N(SiMe3)2}2] (M=Fe, Co), N-heterocyclic carbenes (NHCs) react with primary phosphines to give a series of carbene phosphinidenes of the type (NHC)·PAr. The formation of (IMe4)·PMes (Mes=mesityl) is also catalysed by the phosphinidene-bridged complex [(IMe4)2Fe-(m-PMes)]2, which provides evidence for metal-catalysed phosphinidene \ud transfer.

Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18-c-6 produces [{K(18-c-6)}HAN], which contains the S=1/2 radical [HAN].−. The [HAN].− radical can be transferred to the cobalt(II) amide [Co{N(SiMe3)2}2], forming [K(18-c-6)][(HAN){Co(N′′)2}3]; magnetic measurements on this compound reveal an S=4 spin system with strong cobalt–ligand antiferromagnetic exchange and J≈−290 cm−1 (−2 J formalism). In contrast, the CoII centres in the unreduced analogue [(HAN){Co(N′′)2}3] are weakly coupled (J≈−4.4 cm−1). The finding that [HAN].− can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks.

Reducing hexaazatrinaphthylene (HAN) with potassium in the presence of 18-c-6 produces [{K(18-c-6)}HAN], which contains the S = 1/2 radical [HAN]C ¢ . The [HAN]C ¢ radical can be transferred to the cobalt(II) amide [Co{N- (SiMe3 )2 }2 ], forming [K(18-c-6)][(HAN){Co(N’’)2 }3 ]; magnetic measurements on this compound reveal an S = 4 spin system with strong cobalt–ligand antiferromagnetic exchange and J ¢290 cm¢1 (¢2 J formalism). In contrast, the CoII centres in the unreduced analogue [(HAN){Co(N’’)2}3] are weakly coupled (J ¢4.4 cm¢1 ). The finding that [HAN]C ¢ can be synthesized as a stable salt and transferred to cobalt introduces potential new routes to magnetic materials based on strongly coupled, triangular HAN building blocks. peerReviewed

The structural and bonding properties of a three-coordinate N-heterocyclic silyene (NHSi) complex of the iron(II) amide [Fe{N(SiMe3)2}2] are reported. Computational studies reveal that dispersion forces between the amido SiMe3 substituents and the isopropyl substituents on the NHSi ligand significantly enhance the stability of the complex, along with Fe-to-Si π-backbonding. peerReviewed